Polymerizable compound, polymerizable composition, polymer, optically anisotropic body, and method for producing polymerizable compound

ABSTRACT

A polymerizable compound has a practical low melting point, excellent solubility in a general-purpose solvent, and can produce an optical film at low cost, exhibits low reflected luminance, and achieves uniform conversion of polarized light over a wide wavelength band, an optically anisotropic article. A carbonyl compound is useful as a raw material for producing the polymerizable compound. (In the formula (I), Y 1  to Y 8  represent —C(═O)—O—, G 1  and G 2  represent a C 1-20  divalent linear aliphatic group, Z 1  and Z 2  represent a C 2-10  alkenyl group that is unsubstituted, or substituted with a halogen atom, A x  represents a C 2-30  organic group with at least one aromatic ring, A y  represents a hydrogen atom or C 1-20  alkyl group, A 1  represents a trivalent aromatic group, A 2  and A 3  represent a C 3-30  divalent alicyclic hydrocarbon group, A 4  and A 5  represent a C 6-30  divalent aromatic group or the like, and Q 1  represents a hydrogen atom.)

TECHNICAL FIELD

The invention relates to a polymerizable compound, a polymerizablecomposition, and a polymer that may produce an optical film thatachieves uniform conversion of polarized light over a wide wavelengthband, an optically anisotropic article, a carbonyl compound that isuseful as a raw material for producing the polymerizable compound, amethod for producing the polymerizable compound using the carbonylcompound, and a method for using the carbonyl compound as a raw materialfor producing the polymerizable compound.

A flat panel display (FPD) that utilizes an optical film (e.g.,polarizer and retardation film) can achieve high-resolution display, andhas been widely used as a display device (e.g., TV) that exhibitsexcellent performance.

Examples of the retardation film include a quarter-wave plate thatconverts linearly polarized light into circularly polarized light, ahalf-wave plate that converts the plane of vibration of linearlypolarized light by 90°, and the like. These retardation films canachieve accurate conversion of specific monochromatic light so that ¼λor ½λ retardation occurs.

However, known retardation films have a problem in that polarized lightthat passes through is converted into colored polarized light.Specifically, since a material that forms the retardation film haswavelength dispersion with respect to retardation, and a polarizationstate distribution corresponding to each wavelength occurs with respectto white light that includes different light beams in the visibleregion, it is impossible to achieve accurate ¼λ or ½λ retardation overthe entire wavelength band.

In order to solve the above problem, various wideband retardation filmsthat can achieve uniform retardation with respect to light over a widewavelength band (i.e., retardation films having reverse wavelengthdispersion) have been studied (see Patent Documents 1 to 6, forexample).

It has been desired to reduce the thickness of the flat panel display asmuch as possible along with an improvement in performance and widespreaduse of mobile information terminals (e.g., mobile personal computer andmobile phone). Therefore, a reduction in thickness of the retardationfilm has also been desired.

It has been considered that it is most effective to produce aretardation film by applying a polymerizable composition that includes alow-molecular-weight polymerizable compound to a film substrate in orderto reduce the thickness of the retardation film. Variouslow-molecular-weight polymerizable compounds having excellent wavelengthdispersion, and various polymerizable compositions using suchpolymerizable compounds have been developed (see Patent Documents 7 to24, for example).

However, the low-molecular-weight polymerizable compounds or thepolymerizable compositions disclosed in Patent Documents 7 to 24 have anumber of problems in that it may be difficult to apply thelow-molecular-weight polymerizable compound or the polymerizablecomposition to a film due to a high melting point that is not suitablefor an industrial process, or the temperature range in which liquidcrystallinity is obtained may be very narrow, or solubility in a solventgenerally used for an industrial process may be low, or a polymer filmobtained by polymerizing the low-molecular-weight polymerizable compoundor the polymerizable composition may has insufficient reverse wavelengthdispersion. Moreover, since the above low-molecular-weight polymerizablecompounds and the like are synthesized by performing a plurality ofsteps using a synthesis method that utilizes an expensive reagent, theproduction cost increases.

RELATED-ART DOCUMENT Patent Document Patent Document 1: JP-A-10-68816Patent Document 2: JP-A-10-90521 Patent Document 3: JP-A-11-52131 PatentDocument 4: JP-A-2000-284126 (US20020159005A1) Patent Document 5:JP-A-2001-4837 Patent Document 6: WO2000/026705 Patent Document 7:JP-A-2002-267838 Patent Document 8: JP-A-2003-160540 (US20030102458A1)Patent Document 9: JP-A-2005-208414 Patent Document 10: JP-A-2005-208415Patent Document 11: JP-A-2005-208416 Patent Document 12:JP-A-2005-289980 (US20070176145A1) Patent Document 13: JP-A-2006-330710(US20090072194A1) Patent Document 14: JP-A-2009-179563 (US20090189120A1)Patent Document 15: JP-A-2010-31223 Patent Document 16: JP-A-2011-6360Patent Document 17: JP-A-2011-6361 Patent Document 18: JP-A-2011-42606Patent Document 19: JP-T-2010-537954 (US20100201920A1) Patent Document20: JP-T-2010-537955 (US20100301271A1) Patent Document 21: WO2006/052001(US20070298191A1)

Patent Document 22: U.S. Pat. No. 6,139,771Patent Document 23: U.S. Pat. No. 6,203,724Patent Document 24: U.S. Pat. No. 5,567,349

SUMMARY OF THE INVENTION Technical Problem

The invention was conceived in view of the above situation. An object ofthe invention is to provide a polymerizable compound, a polymerizablecomposition, and a polymer that have a practical low melting point,exhibit excellent solubility in a general-purpose solvent, and canproduce an optical film that can be produced at low cost, exhibits lowreflected luminance, and achieves uniform conversion of polarized lightover a wide wavelength band, an optically anisotropic article, acarbonyl compound that is useful as a raw material for producing thepolymerizable compound, a method for producing the polymerizablecompound using the carbonyl compound, and a method for using thecarbonyl compound as a raw material for producing the polymerizablecompound.

Solution to Problem

The inventors of the invention conducted extensive studies in order toachieve the above object. As a result, the inventors found that anoptical film that achieves uniform conversion of polarized light over awide wavelength band can be produced at low cost by utilizing anoptically anisotropic article that is produced using a polymer obtainedby polymerizing a polymerizable compound represented by the followingformula (I), or a polymerizable composition that includes thepolymerizable compound and an initiator. This finding has led to thecompletion of the invention.

Several aspects of the invention provide the following polymerizablecompound (see (1) to (7)), polymerizable composition (see (8) and (9)),polymer (see (10) and (11)), optically anisotropic article (see (12)),carbonyl compound (see (13) to (16)), method for producing thepolymerizable compound (see (17)), and method for using the carbonylcompound as a raw material for producing the polymerizable compound (see(18)).

(1) A polymerizable compound represented by the following formula (I),

wherein Y¹ to Y⁸ are independently a chemical single bond, —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,G¹ and G² are independently a substituted or unsubstituted divalentlinear aliphatic group having 1 to 20 carbon atoms that optionallyincludes —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—,—C(═O)—NR²—, —NR²—, or —C(═O)—, provided that a case where the linearaliphatic group includes two or more contiguous —O— or —S— is excluded,R² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,Z¹ and Z² are independently an alkenyl group having 2 to 10 carbon atomsthat is substituted with a halogen atom, or unsubstituted,A^(x) is an organic group having 2 to 30 carbon atoms that includes atleast one aromatic ring selected from the group consisting of anaromatic hydrocarbon ring and a heteroaromatic ring,A^(y) is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedalkynyl group having 2 to 20 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 12 carbon atoms, —C(═O)—R³,—SO₂—R⁴, —C(═S)NH—R⁹, or an organic group having 2 to 30 carbon atomsthat includes at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring and a heteroaromatic ring, R³is a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted alkenyl group having 2 to 20carbon atoms, a substituted or unsubstituted cycloalkyl group having 3to 12 carbon atoms, or an aromatic hydrocarbon group having 5 to 12carbon atoms, R⁴ is an alkyl group having 1 to 20 carbon atoms, analkenyl group having 2 to 20 carbon atoms, a phenyl group, or a4-methylphenyl group, R⁹ is a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, or a substituted orunsubstituted aromatic group having 5 to 20 carbon atoms, provided thatthe aromatic ring included in A^(x) and A^(y) is substituted orunsubstituted, and A^(x) and A^(y) are optionally bonded to each otherto form a ring,A¹ is a substituted or unsubstituted trivalent aromatic group,A² and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms,A⁴ and A⁵ are independently a substituted or unsubstituted divalentaromatic group having 6 to 30 carbon atoms, andQ¹ is a hydrogen atom, or a substituted or unsubstituted alkyl grouphaving 1 to 6 carbon atoms.(2) The polymerizable compound according to (1), wherein the totalnumber of π electrons included in A^(x) and A^(y) is 4 to 24.(3) The polymerizable compound according to (1) or (2), wherein A¹ is asubstituted or unsubstituted trivalent benzene ring group, or asubstituted or unsubstituted trivalent naphthalene ring group.(4) The polymerizable compound according to any one of (1) to (3),wherein Y¹ to Y⁸ are independently a chemical single bond, —O—,—O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.(5) The polymerizable compound according to any one of (1) to (4),wherein Z¹ and Z² are independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.(6) The polymerizable compound according to any one of (1) to (5),wherein G¹ and G² are independently a substituted or unsubstituteddivalent aliphatic group having 1 to 20 carbon atoms that optionallyincludes —O—, —O—C(═O)—, —C(═O)—O—, or —C(═O)—, provided that a casewhere the aliphatic group includes two or more contiguous —O— isexcluded.(7) The polymerizable compound according to any one of (1) to (6),wherein G¹ and G² are independently an alkylene group having 1 to 12carbon atoms.(8) A polymerizable composition including at least one type of thepolymerizable compound according to any one of (1) to (7).(9) A polymerizable composition including at least one type of thepolymerizable compound according to any one of (1) to (7), and aninitiator.(10) A polymer obtained by polymerizing the polymerizable compoundaccording to any one of (1) to (7), or the polymerizable compositionaccording to (8) or (9).(11) The polymer according to (10), the polymer being a liquidcrystalline polymer.(12) An optically anisotropic article including the polymer according to(11).(13) A carbonyl compound represented by the following formula (4),

wherein Y¹ to Y⁸ are independently a chemical single bond, —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,G¹ and G² are independently a substituted or unsubstituted divalentlinear aliphatic group having 1 to 20 carbon atoms that optionallyincludes —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—,—C(═O)—NR²—, —NR²—, or —C(═O)—, provided that a case where the aliphaticgroup includes two or more contiguous —O— or —S— is excluded, R² is ahydrogen atom or an alkyl group having 1 to 6 carbon atoms,Z¹ and Z² are independently an alkenyl group having 2 to 10 carbon atomsthat is unsubstituted, or substituted with a halogen atom,A¹ is a substituted or unsubstituted trivalent aromatic group,A² and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms,A⁴ and A⁵ are independently a substituted or unsubstituted divalentaromatic group having 6 to 30 carbon atoms, andQ¹ is a hydrogen atom, or a substituted or unsubstituted alkyl grouphaving 1 to 6 carbon atoms.(14) The carbonyl compound according to (13), wherein A¹ is asubstituted or unsubstituted trivalent benzene ring group, or asubstituted or unsubstituted trivalent naphthalene ring group.(15) The carbonyl compound according to (13) or (14), wherein A² and A³are independently a substituted or unsubstituted divalent cyclohexylgroup.(16) The carbonyl compound according to any one of (13) to (15), whereinZ¹ and Z² are independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.(17) A method for producing a polymerizable compound represented by thefollowing formula (I), the method including reacting the carbonylcompound according to any one of (13) to (16) with a hydrazine compoundrepresented by the following formula,

wherein A^(x) is an organic group having 2 to 30 carbon atoms thatincludes at least one aromatic ring selected from the group consistingof an aromatic hydrocarbon ring and a heteroaromatic ring,A^(y) is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedalkynyl group having 1 to 20 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 12 carbon atoms, —C(═O)—R³,—SO₂—R⁴, —C(═S)NH—R⁹, or an organic group having 2 to 30 carbon atomsthat includes at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring and a heteroaromatic ring, R³is a substituted or unsubstituted alkyl group having 1 to 20 carbonatoms, a substituted or unsubstituted alkenyl group having 2 to 20carbon atoms, a substituted or unsubstituted cycloalkyl group having 3to 12 carbon atoms, or an aromatic hydrocarbon group having 5 to 12carbon atoms, R⁴ is an alkyl group having 1 to 20 carbon atoms, analkenyl group having 2 to 20 carbon atoms, a phenyl group, or a4-methylphenyl group, R⁹ is a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, or a substituted orunsubstituted aromatic group having 5 to 20 carbon atoms, provided thatthe aromatic ring included in A^(x) and A^(y) is substituted orunsubstituted, and A^(x) and A^(y) are optionally bonded to each otherto form a ring,

wherein A^(x), A^(y), Y¹ to Y⁸, Z¹, Z², G¹, G², A¹ to A⁵, and Q¹ are thesame as defined above.(18) A method for using the carbonyl compound according to any one of(13) to (16) as a raw material for producing a polymerizable compoundrepresented by the following formula (I),

wherein A^(x), A^(y), Y¹ to Y⁸, Z¹, Z², G¹, G², A¹ to A⁵, and Q¹ are thesame as defined above.

Advantageous Effects of the Invention

The polymerizable compound, the polymerizable composition, and thepolymer according to the aspects of the invention have a practical lowmelting point, exhibit excellent solubility in a general-purposesolvent, and can produce an optical film that can be produced at lowcost, exhibits low reflected luminance, and achieves uniform conversionof polarized light over a wide wavelength band.

Since the optically anisotropic article according to the aspect of theinvention is produced using the polymer according to the aspect of theinvention, the optically anisotropic article can be produced at lowcost, exhibits low reflected luminance, and achieves uniform conversionof polarized light over a wide wavelength band.

An antireflective film may be produced by combining the film-likeoptically anisotropic article according to the aspect of the inventionwith a polarizer. The antireflective film may suitably be used toprevent reflection from a touch panel, an organic electroluminescencedevice, and the like.

The carbonyl compound according to the aspect of the invention is usefulas an intermediate for producing the polymerizable compound according tothe aspect of the invention.

The method for producing a polymerizable compound according to theaspect of the invention can efficiently produce the polymerizablecompound according to the aspect of the invention.

It is possible to easily produce the polymerizable compound according tothe aspect of the invention in high yield by utilizing the carbonylcompound according to the aspect of the invention as a raw material.

DESCRIPTION OF EMBODIMENTS

A polymerizable compound, a polymerizable composition, a polymer, anoptically anisotropic article, a carbonyl compound, a method forproducing a polymerizable compound, and a method for using a carbonylcompound as a raw material for producing a polymerizable compoundaccording to exemplary embodiments of the invention are described indetail below. Note that the expression “substituted or unsubstituted”used herein in connection with a group or the like means that the groupor the like is unsubstituted, or substituted with a substituent.

1) Polymerizable Compound

A polymerizable compound according to one embodiment of the invention isa compound represented by the formula (I).

Y¹ to Y⁸ in the formula (1) are independently a chemical single bond,—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—.

R¹ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R¹include a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentylgroup, an n-hexyl group, and the like.

R¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbonatoms.

It is preferable that Y¹ to Y⁶ included in the polymerizable compoundaccording to one embodiment of the invention be independently a chemicalsingle bond, —O—, —O—C(═O)—, —C(═O)—O—, or —O—C(═O)—O—.

G¹ and G² are independently a substituted or unsubstituted divalentaliphatic group having 1 to 20 carbon atoms.

Examples of the divalent aliphatic group having 1 to 20 carbon atomsinclude divalent aliphatic groups having a linear structure, such as analkylene group having 1 to 20 carbon atoms and an alkenylene grouphaving 2 to 20 carbon atoms; divalent aliphatic groups such as acycloalkanediyl group having 3 to 20 carbon atoms, a cycloalkenediylgroup having 4 to 20 carbon atoms, and a divalent fused alicyclic grouphaving 10 to 30 carbon atoms; and the like.

Examples of a substituent that may substitute the divalent aliphaticgroup represented by G¹ and G² include halogen atoms such as a fluorineatom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groupshaving 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, ann-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxygroup, a t-butoxy group, an n-pentyloxy group, and an n-hexyloxy group;and the like. Among these, a fluorine atom, a methoxy group, and anethoxy group are preferable.

The aliphatic group optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)—, provided thata case where the aliphatic group includes two or more contiguous —O— or—S— is excluded. R² is a hydrogen atom or an alkyl group having 1 to 6carbon atoms similar to that represented by R¹, and is preferably ahydrogen atom or a methyl group.

—O—, —O—C(═O)—, —C(═O)—O—, and —C(═O)— are preferable as the group thatis optionally included in the aliphatic group.

Specific examples of the aliphatic group that includes the above groupinclude —CH₂—CH₂—O—CH₂—CH₂—, —CH₂—CH₂—S—CH₂—CH₂—,—CH₂—CH₂—O—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—C(═O)—O—CH₂—, —CH₂—O—C(═O)—O—CH₂—CH₂—,—CH₂—CH₂—NR²—C(═O)—CH₂—CH₂—, —CH₂—CH₂—C(═O)—NR²—CH₂—, —CH₂—NR²—CH₂—CH₂—,—CH₂—C(═O)—CH₂—, and the like.

It is preferable that G¹ and G² be independently a divalent aliphaticgroup having a linear structure (e.g., an alkylene group having 1 to 20carbon atoms or an alkenylene group having 2 to 20 carbon atoms), morepreferably an alkylene group having 1 to 12 carbon atoms (e.g.,methylene group, ethylene group, trimethylene group, propylene group,tetramethylene group, pentamethylene group, hexamethylene group,octamethylene group, or decamethylene group (—(CH₂)₁₀—)), andparticularly preferably a tetramethylene group (—(CH₂)₄—), ahexamethylene group (—(CH₂)₆—), an octamethylene group (—(CH₂)₈—), or adecamethylene group (—(CH₂)₁₀—), in order to more advantageously achievethe intended effects of the invention.

Z¹ and Z² are independently an alkenyl group having 2 to 10 carbon atomsthat is unsubstituted, or substituted with a halogen atom.

The number of carbon atoms of the alkenyl group is preferably 2 to 6.Examples of the halogen atom that may substitute the alkenyl grouprepresented by Z¹ and Z² include a fluorine atom, a chlorine atom, abromine atom, and the like. Among these, a chlorine atom is preferable,

Specific examples of the alkenyl group having 2 to 10 carbon atomsrepresented by Z¹ and Z² include CH₂═CH—, CH₂═C(CH₃)—, CH₂═CH—CH₂—,CH₃—CH═CH—, CH₂═CH—CH₂—CH₂—, CH₂═C(CH₃)—CH₂—CH₂—, (CH₃)₂C═CH—CH₂—,(CH₃)₂C═CH—CH₂—CH₂—, CH₂═C(Cl)—, CH₂═C(CH₃)—CH₂—, CH₃—CH═CH—CH₂—, andthe like.

It is preferable that Z¹ and Z² be independently CH₂═CH—, CH₂═C(CH₃)—,CH₂═C(Cl)—, CH₂═CH—CH₂—, CH₂═C(CH₃)—CH₂—, or CH₂═C(CH₃)—CH₂—CH₂—, morepreferably CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—, and still morepreferably CH₂═CH—, in order to more advantageously achieve the intendedeffects of the invention.

A^(x) is an organic group having 2 to 30 carbon atoms that includes atleast one aromatic ring selected from the group consisting of anaromatic hydrocarbon ring and a heteroaromatic ring.

The term “aromatic ring” used herein refers to a cyclic structure thatexhibits aromaticity in a broad sense according to Huckel's rule (i.e.,a cyclic conjugated structure that includes (4n+2) π electrons, and astructure that exhibits aromaticity in which lone pairs of heteroatoms(e.g., sulfur, oxygen, or nitrogen) are involved in the n electronsystem (e.g., thiophene, furan, and benzothiazole).

The organic group having 2 to 30 carbon atoms represented by A^(x) thatincludes at least one aromatic ring selected from the group consistingof an aromatic hydrocarbon ring and a heteroaromatic ring, may include aplurality of aromatic rings, and may include an aromatic hydrocarbonring and a heteroaromatic ring.

Examples of the aromatic hydrocarbon ring include a benzene ring, anaphthalene ring, an anthracene ring, and the like. Examples of theheteroaromatic ring include monocyclic heteroaromatic rings such as apyrrole ring, a furan ring, a thiophene ring, a pyridine ring, apyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, animidazole ring, an oxazole ring, and a thiazole ring; fusedheteroaromatic rings such as a benzothiazole ring, a benzoxazole ring, aquinoline ring, a phthalazine ring, a benzimidazole ring, abenzopyrazole ring, a benzofuran ring, a benzothiophene ring, athiazolopyridine ring, an oxazolopyridine ring, a thiazolopyrazine ring,an oxazolopyrazine ring, a thiazolopyridazine ring, an oxazolopyridazinering, a thiazolopyrimidine ring, and an oxazolopyrimidine ring; and thelike.

The aromatic ring included in A^(x) may be substituted with asubstituent. Examples of the substituent include halogen atoms such as afluorine atom and a chlorine atom; a cyano group; alkyl groups having 1to 6 carbon atoms such as a methyl group, an ethyl group, and a propylgroup; alkenyl groups having 2 to 6 carbon atoms such as a vinyl groupand an allyl group; alkyl halide groups having 1 to 6 carbon atoms suchas a trifluoromethyl group; substituted amino groups such as adimethylamino group; alkoxy groups having 1 to 6 carbon atoms such as amethoxy group, an ethoxy group, and an isopropoxy group; a nitro group;aryl groups such as a phenyl group and a naphthyl group; —C(═O)—R⁵;—C(═O)—OR⁵; —SO₂R⁶; and the like. R⁵ is an alkyl group having 1 to 20carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or acycloalkyl group having 3 to 12 carbon atoms, and R⁶ is an alkyl grouphaving 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbonatoms, a phenyl group, or a 4-methylphenyl group similar to thatrepresented by R⁴.

The aromatic ring included in A^(x) may be substituted with a pluralityof identical or different substituents, and two adjacent substituentsmay be bonded to each other to form a ring. A ring formed by twoadjacent substituents may be either a monocyclic ring or a fusedpolycyclic ring, and may be either an unsaturated ring or a saturatedring.

Note that the number of carbon atoms (i.e., 2 to 30) of the organicgroup represented by A^(x) refers to the total number of carbon atoms ofthe organic group excluding the number of carbon atoms of a substituent.This also applies to the number of carbon atoms of the organic grouprepresented by A^(y).

Examples of the organic group having 2 to 30 carbon atoms represented byA^(x) that includes at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring and a heteroaromatic ring,include aromatic cyclic hydrocarbon groups; heteroaromatic ring groups;alkyl groups having 3 to 30 carbon atoms that include at least onearomatic ring selected from the group consisting of an aromatichydrocarbon ring and a heteroaromatic ring; alkenyl groups having 4 to30 carbon atoms that include at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring and aheteroaromatic ring; alkynyl groups having 4 to 30 carbon atoms thatinclude at least one aromatic ring selected from the group consisting ofan aromatic hydrocarbon ring and a heteroaromatic ring; and the like.

Specific examples of the organic group represented by A^(x) are shownbelow. Note that the organic group represented by A^(x) is not limitedto the following groups. “-” in the following formulas is a bond thatextends from an arbitrary position of the ring (hereinafter the same).

wherein E is NR⁶, an oxygen atom, or a sulfur atom, and R⁶ is a hydrogenatom, or an alkyl group having 1 to 6 carbon atoms (e.g., methyl group,ethyl group, or propyl group).

wherein X, Y, and Z are independently NR⁷, an oxygen atom, a sulfuratom, —SO—, or —SO₂—, provided that a case where two or more oxygenatoms, sulfur atoms, —SO—, or —SO₂— are situated at contiguous positionsis excluded, and R⁷ is a hydrogen atom, or an alkyl group having 1 to 6carbon atoms (e.g., methyl group, ethyl group, or propyl group) similarto that represented by R⁶.

wherein X is the same as defined above.(3) Alkyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

(4) Alkenyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

(5) Alkynyl group that includes at least one aromatic ring selected fromthe group consisting of an aromatic hydrocarbon ring group and aheteroaromatic ring group

A^(x) is preferably an aromatic hydrocarbon group having 6 to 30 carbonatoms or a heteroaromatic ring group having 4 to 30 carbon atoms. A^(x)is more preferably a group among the groups shown below.

A^(x) is still more preferably a group among the groups shown below.

The ring included in A^(x) may be substituted with a substituent.Examples of the substituent include halogen atoms such as a fluorineatom and a chlorine atom; a cyano group; alkyl groups having 1 to 6carbon atoms such as a methyl group, an ethyl group, and a propyl group;alkenyl groups having 2 to 6 carbon atoms such as a vinyl group and anallyl group; alkyl halide groups having 1 to 6 carbon atoms such as atrifluoromethyl group; substituted amino groups such as a dimethylaminogroup; alkoxy groups having 1 to 6 carbon atoms such as a methoxy group,an ethoxy group, and an isopropoxy group; a nitro group; aryl groupssuch as a phenyl group and a naphthyl group; —C(═O)—R⁸; —C(═O)—OR⁸;—SO₂R⁶; and the like. R⁸ is an alkyl group having 1 to 6 carbon atoms(e.g., methyl group or ethyl group), or an aryl group having 6 to 14carbon atoms (e.g., phenyl group). The substituent is preferably ahalogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms,or an alkoxy group having 1 to 6 carbon atoms.

The ring included in A^(x) may be substituted with a plurality ofidentical or different substituents, and two adjacent substituents maybe bonded to each other to form a ring. A ring formed by two adjacentsubstituents may be either a monocyclic ring or a fused polycyclic ring.

Note that the number of carbon atoms (i.e., 2 to 30) of the organicgroup represented by A^(x) refers to the total number of carbon atoms ofthe organic group excluding the number of carbon atoms of a substituent.This also applies to the number of carbon atoms of the organic grouprepresented by A^(y).

A^(y) is a hydrogen atom, a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, a substituted orunsubstituted alkynyl group having 2 to 20 carbon atoms, —C(═O)—R³,—SO₂—R⁴, —C(═S)NH—R⁹, or an organic group having 2 to 30 carbon atomsthat includes at least one aromatic ring selected from the groupconsisting of aromatic hydrocarbon rings and heteroaromatic rings. R³ isa substituted or unsubstituted alkyl group having 1 to 20 carbon atoms,a substituted or unsubstituted alkenyl group having 2 to 20 carbonatoms, a substituted or unsubstituted cycloalkyl group having 3 to 12carbon atoms, or an aromatic hydrocarbon group having 5 to 12 carbonatoms, R⁴ is an alkyl group having 1 to 20 carbon atoms, an alkenylgroup having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenylgroup, and R⁹ is a substituted or unsubstituted alkyl group having 1 to20 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 20 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 12 carbon atoms, or a substituted or unsubstituted aromaticgroup having 5 to 20 carbon atoms.

Examples of the (unsubstituted) alkyl group having 1 to 20 carbon atomsrepresented by A^(y) include a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group, a1-methylpentyl group, a 1-ethylpentyl group, a sec-butyl group, at-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group,an n-hexyl group, an isohexyl group, an n-heptyl group, an n-octylgroup, an n-nonyl group, an n-decyl group, an n-undecyl group, ann-dodecyl group, an n-tridecyl group, an n-tetradecyl group, ann-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, ann-octadecyl group, an n-nonadecyl group, an n-icosyl group, and thelike. The number of carbon atoms of the substituted or unsubstitutedalkyl group having 1 to 20 carbon atoms is preferably 1 to 12, and morepreferably 4 to 10.

Examples of the (unsubstituted) alkenyl group having 2 to 20 carbonatoms represented by A^(y) include a vinyl group, a propenyl group, anisopropenyl group, a butenyl group, an isobutenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a decenylgroup, an undecenyl group, a dodecenyl group, a tridecenyl group, atetradecenyl group, a pentadecenyl group, a hexadecenyl group, aheptadecenyl group, an octadecenyl group, a nonadecenyl group, anicosenyl group, and the like.

The number of carbon atoms of the substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms is preferably 2 to 12.

Examples of the (unsubstituted) cycloalkyl group having 3 to 12 carbonatoms represented by A^(y) include a cyclopropyl group, a cyclobutylgroup, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, andthe like.

Examples of the (unsubstituted) alkynyl group having 2 to 20 carbonatoms represented by A^(y) include an ethynyl group, a propynyl group, a2-propynyl group (propargyl group), a butynyl group, a 2-butynyl group,a 3-butynyl group, a pentynyl group, a 2-pentynyl group, a hexynylgroup, a 5-hexynyl group, a heptynyl group, an octynyl group, a2-octynyl group, a nonanyl group, a decanyl group, a 7-decanyl group,and the like.

Examples of a substituent that may substitute the substituted orunsubstituted alkyl group having 1 to 20 carbon atoms and thesubstituted or unsubstituted alkenyl group having 2 to 20 carbon atomsrepresented by A^(y) include halogen atoms such as a fluorine atom and achlorine atom; a cyano group; substituted amino groups such as adimethylamino group; alkoxy groups having 1 to 20 carbon atoms, such asa methoxy group, an ethoxy group, an isopropoxy group, and a butoxygroup; alkoxy groups having 1 to 12 carbon atoms that are substitutedwith an alkoxy group having 1 to 12 carbon atoms, such as amethoxymethoxy group and a methoxyethoxy group; a nitro group; arylgroups such as a phenyl group and a naphthyl group; cycloalkyl groupshaving 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentylgroup, and a cyclohexyl group; cycloalkyloxy groups having 3 to 8 carbonatoms, such as a cyclopentyloxy group and a cyclohexyloxy group; cyclicether groups having 2 to 12 carbon atoms, such as a tetrahydrofuranylgroup, a tetrahydropyranyl group, a dioxoranyl group, and a dioxanylgroup; aryloxy groups having 6 to 14 carbon atoms, such as a phenoxygroup and a naphthoxy group; fluoroalkoxy group having 1 to 12 carbonatoms in which at least one hydrogen atom is substituted with a fluorineatom, such as a trifluoromethyl group, a pentafluoroethyl group, and—CH₂CF₃; a benzofuryl group; a benzopyranyl group; a benzodioxolylgroup; a benzodioxanyl group; —C(═O)—R⁷; —C(═O)—OR⁷; —SO₂R⁸; —SR¹⁰;alkoxy groups having 1 to 12 carbon atoms that are substituted with—SR¹⁰; a hydroxyl group; and the like. R⁷ and R¹⁰ are independently analkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or anaromatic hydrocarbon group having 6 to 20 carbon atoms, and R⁶ is analkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a phenyl group, or a 4-methylphenyl group similar to thatrepresented by R⁴.

Examples of a substituent that may substitute the substituted orunsubstituted cycloalkyl group having 3 to 12 carbon atoms representedby A^(y) include halogen atoms such as a fluorine atom and a chlorineatom; a cyano group; substituted amino groups such as a dimethylaminogroup; alkyl groups having 1 to 6 carbon atoms, such as a methyl group,an ethyl group, and a propyl group; alkoxy groups having 1 to 6 carbonatoms, such as a methoxy group, an ethoxy group, and an isopropoxygroup; a nitro group; aryl groups such as a phenyl group and a naphthylgroup; cycloalkyl groups having 3 to 8 carbon atoms, such as acyclopropyl group, a cyclopentyl group, and a cyclohexyl group;—C(═O)—R⁷; —C(═O)—OR⁷; —SO₂R⁴; a hydroxyl group; and the like. R⁷ and R⁸are the same as defined above.

Examples of a substituent that may substitute the substituted orunsubstituted alkynyl group having 2 to 20 carbon atoms represented byA^(y) include those mentioned above in connection with the substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, and thesubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms.

R³ included in the group represented by —C(═O)—R³ that may berepresented by A^(y) is a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, or an aromatic hydrocarbongroup having 5 to 12 carbon atoms. Specific examples of these groupsinclude those mentioned above in connection with the substituted orunsubstituted alkyl group having 1 to 20 carbon atoms, the substitutedor unsubstituted alkenyl group having 2 to 20 carbon atoms, and thesubstituted or unsubstituted cycloalkyl group having 3 to 12 carbonatoms represented by A^(y).

R⁴ included in the group represented by —SO₂—R⁴ that may be representedby A^(y) is an alkyl group having 1 to 20 carbon atoms, an alkenyl grouphaving 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group.

Specific examples of the alkyl group having 1 to 20 carbon atoms and thealkenyl group having 2 to 20 carbon atoms represented by R⁴ includethose mentioned above in connection with the alkyl group having 1 to 20carbon atoms and the alkenyl group having 2 to 20 carbon atomsrepresented by A^(y).

Examples of the organic group having 2 to 30 carbon atoms represented byA^(y) that includes at least one aromatic ring selected from the groupconsisting of an aromatic hydrocarbon ring and a heteroaromatic ring,include those mentioned above in connection with A^(x).

A^(y) is preferably a hydrogen atom, a substituted or unsubstitutedalkyl group having 1 to 20 carbon atoms, a substituted or unsubstitutedalkenyl group having 2 to 20 carbon atoms, a substituted orunsubstituted cycloalkyl group having 3 to 12 carbon atoms, asubstituted or unsubstituted alkynyl group having 2 to 20 carbon atoms,—C(═O)—R³, —SO₂—R⁴, or an organic group having 2 to 30 carbon atoms thatincludes at least one aromatic ring selected from the group consistingof an aromatic hydrocarbon ring and a heteroaromatic ring, and morepreferably a hydrogen atom, a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, a substituted orunsubstituted alkynyl group having 2 to 20 carbon atoms, a substitutedor unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms,a substituted or unsubstituted heteroaromatic ring group having 3 to 9carbon atoms, —C(═O)—R³, or —SO₂—R⁴. Note that R³ and R⁴ are the same asdefined above.

Examples of a preferable substituent that may substitute the substitutedor unsubstituted alkyl group having 1 to 20 carbon atoms, thesubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms,or the substituted or unsubstituted alkynyl group having 2 to 20 carbonatoms represented by A^(y), include halogen atoms, a cyano group, alkoxygroups having 1 to 20 carbon atoms, alkoxy groups having 1 to 12 carbonatoms that are substituted with an alkoxy group having 1 to 12 carbonatoms, a phenyl group, a cyclohexyl group, cyclic ether groups having 2to 12 carbon atoms, aryloxy groups having 6 to 14 carbon atoms, ahydroxyl group, a benzodioxanyl group, a phenylsulfonyl group, a4-methylphenylsulfonyl group, a benzoyl group, and —SR¹⁰. Note that R¹⁰is the same as defined above.

Examples of a preferable substituent that may substitute the substitutedor unsubstituted cycloalkyl group having 3 to 12 carbon atoms, thesubstituted or unsubstituted aromatic hydrocarbon group having 6 to 12carbon atoms, or the substituted or unsubstituted heteroaromatic ringgroup having 3 to 9 carbon atoms represented by A^(y), include afluorine atom, alkyl groups having 1 to 6 carbon atoms, alkoxy groupshaving 1 to 6 carbon atoms, and a cyano group.

A^(x) and A^(y) are optionally bonded to each other to form a ring.Examples of such a ring include a substituted or unsubstitutedunsaturated hetero ring having 4 to 30 carbon atoms, and a substitutedor unsubstituted unsaturated carbon ring having 6 to 30 carbon atoms.

The unsaturated hetero ring having 4 to 30 carbon atoms and theunsaturated carbon ring having 6 to 30 carbon atoms are not particularlylimited, and may or may not have aromaticity. Examples of theunsaturated hetero ring having 4 to 30 carbon atoms and the unsaturatedcarbon ring having 6 to 30 carbon atoms are shown below.

Note that the rings shown below correspond to the above part in theformula (I).

wherein X, Y, and Z are the same as defined above.

These rings may be substituted with a substituent. Examples of thesubstituent include those mentioned above in connection with asubstituent that may substitute the aromatic ring included in A^(x).

The total number of π electrons included in A^(x) and A^(y) ispreferably 4 to 24, more preferably 6 to 20, and still more preferably 6to 18, in order to more advantageously achieve the intended effects ofthe invention.

Examples of a preferable combination of A^(x) and A^(y) include (α) acombination wherein A^(x) is an aromatic hydrocarbon group or aheteroaromatic ring group having 4 to 30 carbon atoms, and A^(y) is ahydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, anaromatic hydrocarbon group having 6 to 12 carbon atoms that isoptionally substituted with a halogen atom, a cyano group, an alkylgroup having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbonatoms, or a cycloalkyl group having 3 to 8 carbon atoms, aheteroaromatic ring group having 3 to 9 carbon atoms that is optionallysubstituted with a halogen atom, an alkyl group having 1 to 6 carbonatoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group, asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms,or a substituted or unsubstituted alkynyl group having 2 to 20 carbonatoms, wherein a substituent that may substitute the alkyl group, thealkenyl group, or the alkynyl group is a halogen atom, a cyano group, analkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12carbon atoms that is substituted with an alkoxy group having 1 to 12carbon atoms, a phenyl group, a cyclohexyl group, a cyclic ether grouphaving 2 to 12 carbon atoms, an aryloxy group having 6 to 14 carbonatoms, a hydroxyl group, a benzodioxanyl group, a benzenesulfonyl group,a benzoyl group, or —SR¹⁰, and (β) A^(x) and A^(y) are bonded to eachother to form an unsaturated heterocyclic ring or an unsaturated carbonring. Note that R¹⁰ is the same as defined above.

Examples of a more preferable combination of A^(x) and A^(y) include (γ)a combination wherein A^(x) is a group among the groups respectivelyhaving the following structures, and A^(y) is a hydrogen atom, acycloalkyl group having 3 to 8 carbon atoms, an aromatic hydrocarbongroup having 6 to 12 carbon atoms that is optionally substituted with ahalogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms,an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having3 to 8 carbon atoms, a heteroaromatic ring group having 3 to 9 carbonatoms that is optionally substituted with a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or a cyano group, a substituted or unsubstituted alkyl group having 1 to20 carbon atoms, a substituted or unsubstituted alkenyl group having 2to 20 carbon atoms, or a substituted or unsubstituted alkynyl grouphaving 2 to 20 carbon atoms, wherein a substituent that may substitutethe alkyl group, the alkenyl group, or the alkynyl group is a halogenatom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, analkoxy group having 1 to 12 carbon atoms that is substituted with analkoxy group having 1 to 12 carbon atoms, a phenyl group, a cyclohexylgroup, a cyclic ether group having 2 to 12 carbon atoms, an aryloxygroup having 6 to 14 carbon atoms, a hydroxyl group, a benzodioxanylgroup, a benzenesulfonyl group, a benzoyl group, or —SR¹⁰. Note that R¹⁰is the same as defined above.

wherein X and Y are the same as defined above.

Examples of a particularly preferable combination of A^(x) and A^(y)include (6) a combination wherein AX is a group among the groupsrespectively having the following structures, and A^(y) is a hydrogenatom, a cycloalkyl group having 3 to 8 carbon atoms, an aromatichydrocarbon group having 6 to 12 carbon atoms that is optionallysubstituted with a halogen atom, a cyano group, an alkyl group having 1to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or acycloalkyl group having 3 to 8 carbon atoms, a heteroaromatic ring grouphaving 3 to 9 carbon atoms that is optionally substituted with a halogenatom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having1 to 6 carbon atoms, or a cyano group, a substituted or unsubstitutedalkyl group having 1 to 20 carbon atoms, a substituted or unsubstitutedalkenyl group having 2 to 20 carbon atoms, or a substituted orunsubstituted alkynyl group having 2 to 20 carbon atoms, wherein asubstituent that may substitute the alkyl group, the alkenyl group, orthe alkynyl group is a halogen atom, a cyano group, an alkoxy grouphaving 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atomsthat is substituted with an alkoxy group having 1 to 12 carbon atoms, aphenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxylgroup, a benzodioxanyl group, a benzenesulfonyl group, a benzoyl group,or —SR¹⁰. Note that X is the same as defined above, and R¹⁰ is the sameas defined above.

A¹ is a substituted or unsubstituted trivalent aromatic group. Thetrivalent aromatic group may be a trivalent carbocyclic aromatic group,or may be a trivalent heterocyclic aromatic group. It is preferable thatthe trivalent aromatic group be a trivalent carbocyclic aromatic group,more preferably a trivalent benzene ring group or a trivalentnaphthalene ring group, and still more preferably a trivalent benzenering group or a trivalent naphthalene ring group represented by thefollowing formulas, in order to more advantageously achieve the intendedeffects of the invention.

Note that the substituents Y¹ and Y² are also included in the followingformulas so that the bonding state can be easily understood (Y¹ and Y²are the same as defined above; hereinafter the same).

A¹ is more preferably a group among groups respectively represented bythe following formulas (A11) to (A25), still more preferably a groupamong the groups respectively represented by the formulas (A11), (A13),(A15), (A19), and (A23), and particularly preferably the grouprepresented by the formula (A11) or the group represented by the formula(A23).

Examples of a substituent that may substitute the trivalent aromaticgroup represented by A¹ include those mentioned above in connection witha substituent that may substitute the aromatic ring included in A^(x).It is preferable that A¹ be unsubstituted.

A² and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms.

Examples of the divalent alicyclic hydrocarbon group having 3 to 30carbon atoms include cycloalkanediyl groups having 3 to 30 carbon atoms,divalent fused alicyclic groups having 10 to 30 carbon atoms, and thelike.

Examples of the cycloalkanediyl group having 3 to 30 carbon atomsinclude a cyclopropanediyl group; a cyclobutanediyl group such as acyclobutane-1,2-diyl group and a cyclobutane-1,3-diyl group; acyclopentanediyl group such as a cyclopentane-1,2-diyl group and acyclopentane-1,3-diyl group; a cyclohexanediyl group such as acyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and acyclohexane-1,4-diyl group; a cycloheptanediyl group such as acycloheptane-1,2-diyl group, a cycloheptane-1,3-diyl group, and acycloheptane-1,4-diyl group; a cyclooctanediyl group such as acyclooctane-1,2-diyl group, a cyclooctane-1,3-diyl group, acyclooctane-1,4-diyl group, and a cyclooctane-1,5-diyl group; acyclodecanediyl group such as a cyclodecane-1,2-diyl group, acyclodecane-1,3-diyl group, a cyclodecane-1,4-diyl group, and acyclodecane-1,5-diyl group; a cyclododecanediyl group such as acyclododecane-1,2-diyl group, a cyclododecane-1,3-diyl group, acyclododecane-1,4-diyl group, and a cyclododecane-1,5-diyl group; acyclotetradecanediyl group such as a cyclotetradecane-1,2-diyl group, acyclotetradecane-1,3-diyl group, a cyclotetradecane-1,4-diyl group, acyclotetradecane-1,5-diyl group, and a cyclotetradecane-1,7-diyl group;a cycloeicosanediyl group such as a cycloeicosane-1,2-diyl group and acycloeicosane-1,10-diyl group; and the like.

Examples of the divalent fused alicyclic group having 10 to 30 carbonatoms include a decalindiyl group such as a decalin-2,5-diyl group and adecalin-2,7-diyl group; an adamantanediyl group such as anadamantane-1,2-diyl group and an adamantane-1,3-diyl group; abicyclo[2.2.1]heptanediyl group such as a bicyclo[2.2.1]heptane-2,3-diylgroup, a bicyclo[2.2.1]heptane-2,5-diyl group, and abicyclo[2.2.1]heptane-2,6-diyl group; and the like.

These divalent alicyclic hydrocarbon groups may be substituted with asubstituent at an arbitrary position. Examples of the substituentinclude those mentioned above in connection with a substituent that maysubstitute the aromatic ring included in A^(x).

A² and A³ are preferably a divalent alicyclic hydrocarbon group having 3to 12 carbon atoms, more preferably a cycloalkanediyl group having 3 to12 carbon atoms, still more preferably a group among the groupsrespectively represented by the following formulas (A31) to (A34), andparticularly preferably the group represented by the formula (A32).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms isclassified into a cis-stereoisomer and a trans-stereoisomer based on thedifference in the steric configuration of the carbon atom bonded to Y¹and Y³ (or Y² and Y⁴). For example, a cyclohexane-1,4-diyl group isclassified into a cis-isomer (A32a) and a trans-isomer (A32b) (seebelow).

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms maybe a cis-isomer, a trans-isomer, or a mixture of a cis-isomer and atrans-isomer. Note that it is preferable that the divalent alicyclichydrocarbon group having 3 to 30 carbon atoms be a trans-isomer or acis-isomer, and more preferably a trans-isomer, since an excellentalignment capability can be obtained.

A⁴ and A⁵ are independently a substituted or unsubstituted divalentaromatic group having 6 to 30 carbon atoms.

The aromatic group represented by A⁴ and A⁵ may be a monocyclic aromaticgroup, or may be a polycyclic aromatic group.

Specific examples of a preferable aromatic group represented by A⁴ andA⁵ include the following groups.

The divalent aromatic group represented by A⁴ and A⁵ may be substitutedwith a substituent at an arbitrary position. Examples of the substituentinclude halogen atoms, a cyano group, a hydroxyl group, alkyl groupshaving 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, anitro group, —C(═O)—OR⁸, and the like. Note that R⁸ is an alkyl grouphaving 1 to 6 carbon atoms. Among these, a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbonatoms are preferable as the substituent. A fluorine atom is preferableas the halogen atom. A methyl group, an ethyl group, and a propyl groupare preferable as the alkyl group having 1 to 6 carbon atoms. A methoxygroup and an ethoxy group are preferable as the alkoxy group having 1 to6 carbon atoms.

It is preferable that A⁴ and A⁵ be independently a group among thegroups respectively represented by the following formula (A41), (A42),and (A43) that are optionally substituted with a substituent, andparticularly preferably the group represented by the formula (A41) thatis optionally substituted with a substituent, in order to moreadvantageously achieve the intended effects of the invention.

Q¹ is a hydrogen atom, or a substituted or unsubstituted alkyl grouphaving 1 to 6 carbon atoms.

Examples of the substituted or unsubstituted alkyl group having 1 to 6carbon atoms include those mentioned above in connection with A^(x).

Q¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbonatoms, and more preferably a hydrogen atom or a methyl group.

The polymerizable compound according to one embodiment of the inventionmay be produced by effecting the following reaction, for example.

wherein Y¹ to Y⁸, G¹, G², Z¹, Z², A^(x), A^(y), A¹ to A⁵, and Q¹ are thesame as defined above.

Specifically, the polymerizable compound represented by the formula (I)can be produced with high selectivity in high yield by reacting thehydrazine compound represented by the formula (3) (hydrazine compound(3)) with the carbonyl compound represented by the formula (4) (carbonylcompound (4)) in a molar ratio (hydrazine compound (3):carbonyl compound(4)) of 1:2 to 2:1 (preferably 1:1.5 to 1.5:1).

The above reaction may be effected in the presence of an acid catalystsuch as an organic acid (e.g., (±)-10-camphorsulfonic acid orp-toluenesulfonic acid), or an inorganic acid (e.g., hydrochloric acidor sulfuric acid). The addition of the acid catalyst may reduce thereaction time, and improve the yield. The acid catalyst is normallyadded in an amount of 0.001 to 1 mol based on 1 mol of the carbonylcompound (4). The acid catalyst may be added directly, or a solutionprepared by dissolving the acid catalyst in an appropriate solvent maybe added.

The solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude alcohol-based solvents such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; ether-based solvents such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; ester-based solvents such as ethyl acetate,propyl acetate, and methyl propionate; aromatic hydrocarbon-basedsolvents such as benzene, toluene, and xylene; aliphatichydrocarbon-based solvents such as n-pentane, n-hexane, and n-heptane;amide-based solvents such as N,N-dimethylformamide, N-methylpyrrolidone,and hexamethylphosphoric triamide; sulfur-containing solvents such asdimethyl sulfoxide and sulfolane; mixed solvents including two or moresolvents among these solvents; and the like.

Among these, alcohol-based solvents, ether-based solvents, and mixedsolvents of an alcohol-based solvent and an ether-based solvent arepreferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of the hydrazinecompound (3).

The reaction proceeds smoothly when the reaction temperature is withinthe range from −10° C. to the boiling point of the solvent. The reactiontime is determined taking account of the reaction scale, but is normallyseveral minutes to several hours.

The hydrazine compound (3) may be produced as shown below.

wherein A^(x) and A^(y) are the same as defined above, and X is aleaving group (e.g., halogen atom, methanesulfonyloxy group, orp-toluenesulfonyloxy group).

Specifically, the compound represented by the formula (2a) is reactedwith the hydrazine (1) in an appropriate solvent in a molar ratio(compound (2a):hydrazine (1)) of 1:1 to 1:20 (preferably 1:2 to 1:10) toobtain the corresponding hydrazine compound (3a), and the hydrazinecompound (3a) is reacted with the compound represented by the formula(2b) to obtain the hydrazine compound (3).

Hydrazine monohydrate is normally used as the hydrazine (1). Acommercially available product may be used directly as the hydrazine(1).

The solvent used for the above reaction is not particularly limited aslong as the solvent is inert to the reaction. Examples of the solventinclude alcohol-based solvents such as methyl alcohol, ethyl alcohol,n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol,sec-butyl alcohol, and t-butyl alcohol; ether-based solvents such asdiethyl ether, tetrahydrofuran, 1,2-dimethoxyethane, 1,4-dioxane, andcyclopentyl methyl ether; aromatic hydrocarbon-based solvents such asbenzene, toluene, and xylene; aliphatic hydrocarbon-based solvents suchas n-pentane, n-hexane, and n-heptane; amide-based solvents such asN,N-dimethylformamide, N-methylpyrrolidone, and hexamethylphosphorictriamide; sulfur-containing solvents such as dimethyl sulfoxide andsulfolane; mixed solvents including two or more solvents among thesesolvents; and the like.

Among these, alcohol-based solvents, ether-based solvents, and mixedsolvents of an alcohol-based solvent and an ether-based solvent arepreferable.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 100 g per gram of hydrazine.

The reaction proceeds smoothly when the reaction temperature is withinthe range from −10° C. to the boiling point of the solvent. The reactiontime is determined taking account of the reaction scale, but is normallyseveral minutes to several hours.

The hydrazine compound (3) may also be produced by reducing thediazonium salt (5) (see below) using a known method.

wherein A^(x) and A^(y) are the same as defined above, and X⁻ is ananion that is a counter ion for diazonium. Examples of the anionrepresented by X⁻ include inorganic anions such as ahexafluorophosphoric acid ion, a fluoroboric acid ion, a chloride ion,and a sulfuric acid ion; organic anions such as apolyfluoroalkylcarboxylic acid ion, a polyfluoroalkylsulfonic acid ion,a tetraphenylboric acid ion, an aromatic carboxylic acid ion, and anaromatic sulfonic acid ion; and the like.

Examples of a reducing agent used for the above reaction include a metalsalt reducing agent.

The term “metal salt reducing agent” normally refers to a compound thatincludes a metal having a small valence, or a compound that includes ametal ion and a hydrido source (see “Yuki Gosei Jikkenhou Handbook(Handbook of Organic Synthesis Experiments)”, 1990, edited by TheSociety of Synthetic Organic Chemistry, Japan, published by Maruzen Co.,Ltd., p. 810).

Examples of the metal salt reducing agent include NaAlH₄,NaAlH_(p)(Or)_(q) (wherein p and q are independently an integer from 1to 3, provided that p+q=4, and r is an alkyl group having 1 to 6 carbonatoms), LiAlH₄, iBu₂AlH, LiBH₄, NaBH₄, SnCl₂, CrCl₂, TiCl₃, and thelike.

The reduction reaction may be effected under known reaction conditions.For example, the reduction reaction may be effected under the reactionconditions described in JP-A-2005-336103, “Shin-Jikken Kagaku Koza (NewExperimental Chemistry Course)”, 1978, Vol. 14, published by MaruzenCo., Ltd., “Jikken Kagaku Koza (Experimental Chemistry Course)”, 1992,Vol. 20, published by Maruzen Co., Ltd., or the like.

The diazonium salt (5) may be produced from aniline or the like using aknown method.

The carbonyl compound (4) may be produced by appropriately bonding andmodifying a plurality of known compounds having a desired structure byarbitrarily combining an ether linkage (—O—)-forming reaction, an esterlinkage (—C(═O)—O— or —O—C(═O)—)-forming reaction, a carbonate linkage(—O—C(═O)—O—)-forming reaction, and an amide linkage (—C(═O)—NH— or—NH—C(═O)—)-forming reaction.

An ether linkage may be formed as described below.

(i) A compound represented by D1-hal (wherein Hal is a halogen atom(hereinafter the same)) and a compound represented by D2-OMet (whereinMet is an alkali metal (mainly sodium) (hereinafter the same)) are mixedand condensed (Williamson synthesis). Note that D1 and D2 are anarbitrary organic group (hereinafter the same).(ii) A compound represented by D1-hal and a compound represented byD2-OH are mixed and condensed in the presence of a base (e.g., sodiumhydroxide or potassium hydroxide).(iii) A compound represented by D1-J (wherein J is an epoxy group) and acompound represented by D2-OH are mixed and condensed in the presence ofa base (e.g., sodium hydroxide or potassium hydroxide).(iv) A compound represented by D1-OFN (wherein OFN is a group thatincludes an unsaturated bond) and a compound represented by D2-OMet aremixed and subjected to an addition reaction in the presence of a base(e.g., sodium hydroxide or potassium hydroxide).(v) A compound represented by D1-hal and a compound represented byD2-OMet are mixed and condensed in the presence of copper or cuprouschloride (Ullmann condensation).

An ester linkage and an amide linkage may be formed as described below.

(vi) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of a dehydration-condensation agent (e.g.,N,N-dicyclohexylcarbodiimide).(vii) A compound represented by D1-COOH is reacted with a halogenatingagent to obtain a compound represented by D1-CO-hal, and the compoundrepresented by D1-CO-hal is reacted with a compound represented by D2-OHor D2-NH₂ in the presence of a base.(viii) A compound represented by D1-COOH is reacted with an acidanhydride to obtain a mixed acid anhydride, and the mixed acid anhydrideis reacted with a compound represented by D2-OH or D2-NH₂.(ix) A compound represented by D1-COOH and a compound represented byD2-OH or D2-NH₂ are subjected to dehydration and condensation in thepresence of an acid catalyst or a base catalyst.

More specifically, the carbonyl compound (4) according to one embodimentof the invention may be produced using the following method (see thefollowing reaction formula).

wherein Y¹ to Y⁸, G¹, G², Z¹, Z², A¹ to A⁵, and Q¹ are the same asdefined above, L¹ and L² are a leaving group (e.g., hydroxyl group,halogen atom, methanesulfonyloxy group, or p-toluenesulfonyloxy group),—Y^(1a) is a group that reacts with -L¹ to form —Y¹—, and —Y^(2a) is agroup that reacts with -L² to form —Y²—.

Specifically, the carbonyl compound (4) according to one embodiment ofthe invention may be produced by sequentially reacting the compoundrepresented by the formula (7a) and the compound represented by theformula (7b) with the compound represented by the formula (6d) using anether linkage (—O—)-forming reaction, an ester linkage (—C(═O)—O— or—O—C(═O)—)-forming reaction, or a carbonate linkage(—O—C(═O)—O—)-forming reaction known in the art.

The carbonyl compound (4) wherein Y¹ is a group represented byY¹¹—C(═O)—O—, and the group represented by Z²—Y-G²-Y⁶-A⁵-Y⁴-A³-Y²— isidentical with the group represented by Z¹-Y⁷-G¹-Y⁵-A⁴-Y³-A²-Y¹—(hereinafter referred to as “compound (4′)”) may be produced as shownbelow.

wherein Y³, Y⁵, Y⁷, G¹, Z¹, A¹, A², A⁴, Q¹, and L¹ are the same asdefined above, Y¹¹ is a group whereby Y¹ is Y¹¹—C(═O)—O—, and Y¹ is thesame as defined above.

Specifically, the dihydroxy compound represented by the formula (6)(compound (6)) is reacted with the compound represented by the formula(7) (compound (7)) in a molar ratio (compound (6):compound (7)) of 1:2to 1:4 (preferably 1:2 to 1:3) to produce the target compound (4′) withhigh selectivity in high yield.

When the compound (7) is a compound (carboxylic acid) represented by theformula (7) wherein L¹ is a hydroxyl group, the target product may beobtained by effecting the reaction in the presence of adehydration-condensation agent (e.g.,1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride ordicyclohexylcarbodiimide).

The dehydration-condensation agent is normally used in an amount of 1 to3 mol based on 1 mol of the compound (7).

When the compound (7) is a compound (carboxylic acid) represented by theformula (7) wherein L¹ is a hydroxyl group, the target product may alsobe obtained by effecting the reaction in the presence of a sulfonylhalide (e.g., methanesulfonyl chloride or p-toluenesulfonyl chloride)and a base (e.g., triethylamine, diisopropylethylamine, pyridine, or4-(dimethylamino)pyridine).

The sulfonyl halide is normally used in an amount of 1 to 3 mol based on1 mol of the compound (7).

The base is normally used in an amount of 1 to 3 mol based on 1 mol ofthe compound (7).

In this case, a compound (mixed acid anhydride) represented by theformula (7) wherein L¹ is a sulfonyloxy group may be isolated, andsubjected to the subsequent reaction.

When the compound (7) is a compound (acid halide) represented by theformula (7) wherein L¹ is a halogen atom, the target product may beobtained by effecting the reaction in the presence of a base.

Examples of the base include organic bases such as triethylamine andpyridine; and inorganic bases such as sodium hydroxide, sodiumcarbonate, and sodium hydrogen carbonate.

The base is normally used in an amount of 1 to 3 mol based on 1 mol ofthe compound (7).

Examples of the solvent used for the above reaction includechlorine-based solvents such as chloroform and methylene chloride;amide-based solvents such as N-methylpyrrolidone, N,N-dimethylformamide,N,N-dimethylacetamide, and hexamethylphosphoric triamide; ether-basedsolvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran,tetrahydropyran, and 1,3-dioxolane; sulfur-containing solvents such asdimethyl sulfoxide and sulfolane; aromatic hydrocarbon-based solventssuch as benzene, toluene, and xylene; aliphatic hydrocarbon-basedsolvents such as n-pentane, n-hexane, and n-octane; alicyclichydrocarbon-based solvents such as cyclopentane and cyclohexane; mixedsolvents of two or more solvents among these solvents; and the like.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 50 g per gram of the hydroxy compound(6).

Many of the compounds (6) are known compounds, and may be produced usinga known method.

For example, the compound (6) may be produced using the following method(see the following reaction formula) (see WO2009/042544 and The Journalof Organic Chemistry, 2011, 76, 8082-8087). A commercially availableproduct may be used as the compound (6) optionally after purification.

wherein A¹ and Q¹ are the same as defined above, A^(1a) is a divalentaromatic group that forms A¹ through formylation or acylation, and R′ isa protecting group for a hydroxyl group, such as an alkyl group having 1to 6 carbon atoms (e.g., methyl group or ethyl group), or an alkoxyalkylgroup having 2 to 6 carbon atoms (e.g., methoxymethyl group).

Specifically, the target compound (6) may be produced by alkylating thehydroxyl groups of the dihydroxy compound represented by the formula(6a) (e.g., 1,4-dihydroxybenzene or 1,4-dihydroxynaphthalene) to obtainthe compound represented by the formula (6b), effecting formylation oracylation at the ortho position with respect to the OR′ group using aknown method to obtain the compound represented by the formula (6c), anddeprotecting (dealkylating) the compound represented by the formula(6c).

A commercially available product may be used as the compound (6) eitherdirectly or after purification.

Most of the compounds (7) are known compounds. The carbonyl compound (7)may be produced by appropriately bonding and modifying a plurality ofknown compounds having a desired structure by arbitrarily combining anether linkage (—O—)-forming reaction, an ester linkage (—C(═O)—O— or—O—C(═O)—)-forming reaction, a carbonate linkage (—O—C(═O)—O—)-formingreaction, and an amide linkage (—C(═O)—NH— or —NH—C(═O)—)-formingreaction.

For example, when the compound (7) is a compound represented by thefollowing formula (7′) (compound (7′)), the compound (7) may be producedas shown below using a dicarboxylic acid represented by the formula (9′)(compound (9′)).

wherein Y⁵, Y⁷, G¹, Z¹, A², A⁴, and Y¹¹ are the same as defined above,Y¹² is a group whereby —O—C(═O)—Y¹² is Y³, and R is an alkyl group suchas a methyl group or an ethyl group, or a substituted or unsubstitutedaryl group such as a phenyl group or a p-methylphenyl group.

Specifically, the sulfonyl chloride represented by the formula (10) isreacted with the compound (9′) in the presence of a base (e.g.,triethylamine or 4-(dimethylamino)pyridine).

The compound (8) and a base (e.g., triethylamine or4-(dimethylamino)pyridine) are added to the reaction mixture to effect areaction.

Sulfonyl chloride is normally used in an amount of 0.5 to 0.7equivalents based on 1 equivalent of the compound (9′).

The compound (8) is normally used in an amount of 0.5 to 0.6 equivalentsbased on 1 equivalent of the compound (9′).

The base is normally used in an amount of 0.5 to 0.7 equivalents basedon 1 equivalent of the compound (9′).

The reaction temperature is 20 to 30° C. The reaction time is determinedtaking account of the reaction scale and the like, but is normallyseveral minutes to several hours.

Examples of a solvent used for the above reaction include thosementioned above in connection with the solvent that may be used whenproducing the compound (4′). It is preferable to use an ether as thesolvent.

The solvent may be used in an appropriate amount taking account of thetype of each compound, the reaction scale, and the like. The solvent isnormally used in an amount of 1 to 50 g per gram of the compound (9′).

After completion of the reaction, a post-treatment operation normallyemployed in synthetic organic chemistry is performed, optionallyfollowed by a known separation/purification means such as columnchromatography, recrystallization, or distillation to isolate the targetproduct.

The structure of the target product may be identified by measurement(e.g., NMR spectrometry, IR spectrometry, or mass spectrometry),elemental analysis, or the like.

2) Polymerizable Composition

A polymerizable composition according to one embodiment of the inventionincludes the polymerizable compound according to one embodiment of theinvention, and an initiator. The initiator is used to more efficientlypolymerize the polymerizable composition according to one embodiment ofthe invention.

The initiator may be appropriately selected taking account of the typeof polymerizable group included in the polymerizable compound. Forexample, a radical initiator may be used when the polymerizable group isa radically polymerizable group. An anionic initiator may be used whenthe polymerizable group is an anionically polymerizable group. Acationic initiator may be used when the polymerizable group is acationically polymerizable group.

Examples of the radical initiator include a thermal radical generatorthat is a compound that generates active species that initiatepolymerization of the polymerizable compound upon heating, and aphoto-radical generator that is a compound that generates active speciesthat initiate polymerization of the polymerizable compound upon exposureto exposure light (e.g., visible rays, ultraviolet rays (e.g., i-line),deep ultraviolet rays, electron beams, or X-rays). It is preferable touse the photo-radical generator.

Examples of the photo-radical generator include acetophenone-basedcompounds, biimidazole-based compounds, triazine-based compounds,O-acyloxime-based compounds, onium salt-based compounds, benzoin-basedcompounds, benzophenone-based compounds, α-diketone-based compounds,polynuclear quinone-based compounds, xanthone-based compounds,diazo-based compounds, imide sulfonate-based compounds, and the like.These compounds generate active radicals and/or an active acid uponexposure. These photo-radical generators may be used either alone or incombination.

Specific examples of the acetophenone-based compounds include2-hydroxy-2-methyl-1-phenylpropan-1-one,2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one,1-hydroxycyclohexyl phenyl ketone,2,2-dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione,2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone, and the like,

Specific examples of the biimidazole-based compounds include2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetrakis(4-ethoxycarbonylphenyl)-1,2′-biimidazole,2,2′-bis(2-chlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-trichlorophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2-bromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4-dibromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,2,2′-bis(2,4,6-tribromophenyl)-4,4′,5,5′-tetraphenyl-1,2′-biimidazole,and the like.

When using a biimidazole-based compound as a photoinitiator, it ispreferable to use a hydrogen donor in combination with thebiimidazole-based compound since sensitivity can be further improved.

The term “hydrogen donor” used herein refers to a compound that candonate a hydrogen atom to radicals generated by the biimidazole-basedcompound upon exposure. A mercaptan-based compound, an amine-basedcompound, and the like are preferable as the hydrogen donor.

Examples of the mercaptan-based compound include2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole,2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2,5-dimethylaminopyridine,and the like. Examples of the amine-based compound include4,4′-bis(dimethylamino)benzophenone, 4,4′-bis(diethylamino)benzophenone,4-diethylaminoacetophenone, 4-dimethylaminopropiophenone,ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid,4-dimethylaminobenzonitrile, and the like.

Specific examples of the triazine-based compounds include triazine-basedcompounds that include a halomethyl group, such as2,4,6-tris(trichloromethyl)-s-triazine,2-methyl-4,6-bis(trichloromethyl)-s-triazine,2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine,2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and2-(4-n-butoxyphenyl)-4, 6-bis(trichloromethyl)-s-triazine.

Specific examples of the O-acyloxime-based compounds include1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoyloxime),1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),1-[4-(benzoyl)phenyl]-octane-1,2-dione-2-(O-benzoyloxime),1-[9-ethyl-6-(2-methylbenzoyl)-9h-carbazol-3-yl]-ethanone-1-(O-acetyloxime),1-[9-ethyl-6-(3-methylbenzoyl)-9h-carbazol-3-yl]-ethanone-1-(O-acetyloxime),1-(9-ethyl-6-benzoyl-9h-carbazol-3-yl)-ethanone-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazol-3-yl]-1-(0-acetyloxime),ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)benzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9h-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime),ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-1-(O-acetyloxime),and the like.

A commercially available product may be used directly as thephoto-radical generator. Specific examples of a commercially availablephoto-radical generator include Irgacure 907, Irgacure 184, Irgacure369, Irgacure 651, Irgacure 819, Irgacure 907, Irgacure OXE02(manufactured by BASF); Adekaoptomer N1919 (manufactured by AdekaCorporation); and the like.

Examples of the anionic initiator include alkyllithium compounds;monolithium salts or monosodium salts of biphenyl, naphthalene, pyrene,and the like; polyfunctional initiators such as dilithiums andtrilithium salts; and the like.

Examples of the cationic initiator include proton acids such as sulfuricacid, phosphoric acid, perchloric acid, and trifluoromethanesulfonicacid; Lewis acids such as boron trifluoride, aluminum chloride, titaniumtetrachloride, and tin tetrachloride; an aromatic onium salt or acombination of an aromatic onium salt and a reducing agent; and thelike.

These initiators may be used either alone or in combination.

The initiator is normally used to prepare the polymerizable compositionaccording to one embodiment of the invention in an amount of 0.1 to 30parts by weight, and preferably 0.5 to 10 parts by weight, based on 100parts by weight of the polymerizable compound.

It is preferable to add a surfactant to the polymerizable compositionaccording to one embodiment of the invention in order to adjust surfacetension. The surfactant is not particularly limited, but is preferably anonionic surfactant. A commercially available product may be used as thenonionic surfactant. Examples of the nonionic surfactant include anonionic surfactant that is an oligomer having a molecular weight ofabout several thousand (e.g., “KH-40” manufactured by AGC Seimi ChemicalCo., Ltd.), and the like. The surfactant is normally added to thepolymerizable composition according to one embodiment of the inventionin an amount of 0.01 to 10 parts by weight, and preferably 0.1 to 2parts by weight, based on 100 parts by weight of the polymerizablecompound.

The polymerizable composition according to one embodiment of theinvention may further include an additional additive such as anadditional copolymerizable monomer, a metal, a metal complex, a dye, apigment, a fluorescent material, a phosphorescent material, a levelingagent, a thixotropic agent, a gelling agent, a polysaccharide, a UVabsorber, an IR (infrared) absorber, an antioxidant, an ion-exchangeresin, or a metal oxide (e.g., titanium oxide). Each additive isnormally added to the polymerizable composition according to oneembodiment of the invention in an amount of 0.1 to 20 parts by weightbased on 100 parts by weight of the polymerizable compound.

The polymerizable composition according to one embodiment of theinvention may be prepared by mixing and dissolving given amounts of thepolymerizable compound according to one embodiment of the invention, theinitiator, and an optional additive in an appropriate organic solvent.

Examples of the organic solvent include ketones such as cyclopentanone,cyclohexanone, and methyl ethyl ketone; acetates such as butyl acetateand amyl acetate; halogenated hydrocarbons such as chloroform,dichloromethane, and dichloroethane; ethers such as 1,4-dioxane,cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and1,3-dioxolane; and the like.

The polymerizable composition thus obtained is useful as a raw materialfor producing a polymer according to one embodiment of the invention oran optically anisotropic article according to one embodiment of theinvention (described below).

3) Polymer

A polymer according to one embodiment of the invention is (1) a polymerobtained by polymerizing the polymerizable compound according to oneembodiment of the invention, or (2) a polymer obtained by polymerizingthe polymerizable composition according to one embodiment of theinvention.

The term “polymerization” used herein refers to a chemical reaction in abroad sense including a normal polymerization reaction and acrosslinking reaction.

(1) Polymer Obtained by Polymerizing Polymerizable Compound

The polymer obtained by polymerizing the polymerizable compoundaccording to one embodiment of the invention may be a homopolymer of thepolymerizable compound according to one embodiment of the invention, acopolymer of two or more types of the polymerizable compound accordingto one embodiment of the invention, or a copolymer of the polymerizablecompound according to one embodiment of the invention and an additionalcopolymerizable monomer.

Examples of the additional copolymerizable monomer include, but are notlimited to, 4′-methoxyphenyl 4-(2-methacryloyloxyethyloxy)benzoate,biphenyl 4-(6-methacryloyloxyhexyloxy)benzoate, 4′-cyanobiphenyl4-(2-acryloyloxyethyloxy)benzoate, 4′-cyanobiphenyl4-(2-methacryloyloxyethyloxy)benzoate, 3′,4′-difluorophenyl4-(2-methacryloyloxyethyloxy)benzoate, naphthyl4-(2-methacryloyloxyethyloxy)benzoate, 4-acryloyloxy-4′-decylbiphenyl,4-acryloyloxy-4′-cyanobiphenyl,4-(2-acryloyloxyethyloxy)-4′-cyanobiphenyl,4-(2-methacryloyloxyethyloxy)-4′-methoxybiphenyl,4-(2-methacryloyloxyethyloxy)-4′-(4″-fluorobenzyloxy)-biphenyl,4-acryloyloxy-4′-propylcyclohexylphenyl,4-methacryloyl-4′-butylbicyclohexyl, 4-acryloyl-4′-amyltolan,4-acryloyl-4′-(3,4-difluorophenyl)bicyclohexyl, (4-amylphenyl)4-(2-acryloyloxyethyl)benzoate, (4-(4′-propylcyclohexyl)phenyl)4-(2-acryloyloxyethyl)benzoate, and the like.

Examples of a commercially available product of the additionalcopolymerizable monomer include LC-242 (manufactured by BASF) and thelike. The compounds disclosed in JP-A-2007-002208, JP-A-2009-173893,JP-A-2009-274984, JP-A-2010-030979, JP-A-2010-031223, JP-A-2011-006360,and the like may also be used as the additional copolymerizable monomer.

A polyfunctional monomer that includes a plurality of polymerizableunsaturated groups (e.g., acryloyl group, methacryloyl group, vinylgroup, and allyl group) may also be used as the additionalcopolymerizable monomer.

Examples of such a polyfunctional monomer include alkanediol diacrylatessuch as 1,2-butanediol diacrylate, 1,4-butanediol diacrylate,1,3-butanediol diacrylate, neopentanediol diacrylate, and 1,6-hexanedioldiacrylate, alkanediol dimethacrylates such as 1,2-butanedioldimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanedioldimethacrylate, neopentanediol dimethacrylate, and 1,6-hexanedioldimethacrylate, polyethylene glycol diacrylates such as ethylene glycoldiacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate,and tetraethylene glycol diacrylate, polypropylene glycol diacrylatessuch as propylene glycol diacrylate, dipropylene glycol diacrylate,tripropylene glycol diacrylate, and tetrapropylene glycol diacrylate,polyethylene glycol dimethacrylates such as ethylene glycoldimethacrylate, diethylene glycol dimethacrylate, triethylene glycoldimethacrylate, and tetraethylene glycol dimethacrylate, polypropyleneglycol dimethacrylates such as propylene glycol dimethacrylate,dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate,and tetrapropylene glycol dimethacrylate, polyethylene glycol divinylethers such as ethylene glycol divinyl ether, diethylene glycol divinylether, triethylene glycol divinyl ether, and tetraethylene glycoldivinyl ether, polyethylene glycol diallyl ethers such as ethyleneglycol diallyl ether, diethylene glycol diallyl ether, triethyleneglycol diallyl ether, and tetraethylene glycol diallyl ether, bisphenolF ethoxylate diacrylate, bisphenol F ethoxylate dimethacrylate,bisphenol A ethoxylate diacrylate, bisphenol A ethoxylatedimethacrylate, trimethylolpropane triacrylate, trimethylolpropanetrimethacrylate, trimethylolpropane ethoxylate triacrylate,trimethylolpropane ethoxylate trimethacrylate, trimethylolpropanepropoxylate triacrylate, trimethylolpropane propoxylate trimethacrylate,isocyanuric acid ethoxylate triacrylate, glycerol ethoxylatetriacrylate, glycerol propoxylate triacrylate, pentaerythritolethoxylate tetraacrylate, ditrimethylolpropane ethoxylate tetraacrylate,dipentaerythritol ethoxylate hexacrylate, and the like.

The polymerizable compound according to one embodiment of the inventionmay be (co)polymerized optionally together with the additionalcopolymerizable monomer in the presence of an appropriate initiator. Theinitiator may be used in an amount similar to that of the initiatorincluded in the polymerizable composition.

When the polymer according to one embodiment of the invention is acopolymer of the polymerizable compound according to one embodiment ofthe invention and the additional copolymerizable monomer, the content ofstructural units derived from the polymerizable compound according toone embodiment of the invention is not particularly limited, but ispreferably 50 wt % or more, and more preferably 70 wt % or more, basedon the total structural units. When the content of structural unitsderived from the polymerizable compound is within the above range, apolymer that has a high glass transition temperature (Tg) and highhardness can be obtained.

The polymer (1) may be produced by (A) (co)polymerizing thepolymerizable compound optionally together with the additionalcopolymerizable monomer in an appropriate organic solvent in thepresence of an appropriate initiator, isolating the target polymer,dissolving the polymer in an appropriate organic solvent to prepare asolution, applying the solution to an appropriate substrate to obtain afilm, and drying the film, followed by optional heating, or (B) applyinga solution prepared by dissolving the polymerizable compound in anorganic solvent optionally together with the additional copolymerizablemonomer to a substrate using a known coating method, removing thesolvent, and effecting polymerization by applying heat or activatedenergy rays, for example.

Examples of the initiator include those mentioned above in connectionwith the initiator included in the polymerizable composition.

The organic solvent used for polymerization when using the method (A) isnot particularly limited as long as the organic solvent is inert.Examples of the organic solvent include aromatic hydrocarbons such astoluene, xylene, and mesitylene; ketones such as cyclohexanone,cyclopentanone, and methyl ethyl ketone; acetates such as butyl acetateand amyl acetate; halogenated hydrocarbons such as chloroform,dichloromethane, and dichloroethane; ethers such as cyclopentyl methylether, tetrahydrofuran, and tetrahydropyran; and the like. Among these,it is preferable to use a compound having a boiling point of 60 to 250°C., and preferably 60 to 150° C., from the viewpoint of handlingcapability.

Examples of the organic solvent used to dissolve the polymer in themethod (A) and the organic solvent used for the method (B) includeketone-based solvents such as acetone, methyl ethyl ketone, methylisobutyl ketone, cyclopentanone, and cyclohexanone; ester-based solventssuch as butyl acetate and amyl acetate; halogenated hydrocarbon-basedsolvents such as dichloromethane, chloroform, and dichloroethane;ether-based solvents such as tetrahydrofuran, tetrahydropyran,1,2-dimethoxyethane, 1,4-dioxane, cyclopentyl methyl ether,1,3-dioxolane; aprotic polar solvents such as N,N-dimethylformamide,N,N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, andN-methylpyrrolidone; and the like. Among these, it is preferable to usea compound having a boiling point of 60 to 200° C. from the viewpoint ofhandling capability. These solvents may be used either alone or incombination.

A substrate formed of a known organic or inorganic material may be usedas the substrate. Examples of the organic material includepolycycloolefins (e.g., Zeonex and Zeonor (registered trademark;manufactured by Zeon Corporation); Arton (registered trademark;manufactured by JSR Corporation); and Apel (registered trademark;manufactured by Mitsui Chemicals Inc.)), polyethylene terephthalate,polycarbonate, polyimide, polyamide, polymethyl methacrylate,polystyrene, polyvinyl chloride, polytetrafluoroethylene, cellulose,cellulose triacetate, polyethersulfone, and the like. Examples of theinorganic material include silicon, glass, calcite, and the like. It ispreferable to use an organic material.

The substrate may be a single-layer substrate, or may be a laminate.

The substrate is preferably a substrate formed of an organic material,and more preferably a resin film formed of the organic material.

The polymer solution (method (A)) or the solution that is subjected topolymerization (method (B)) may be applied to the substrate using aknown coating method. Examples of the coating method include a curtaincoating method, an extrusion coating method, a roll coating method, aspin coating method, a dip coating method, a bar coating method, a spraycoating method, a slide coating method, a print coating method, and thelike.

(2) Polymer Obtained by Polymerizing Polymerizable Composition

The polymer according to one embodiment of the invention can be easilyobtained by polymerizing the polymerizable composition according to oneembodiment of the invention. It is preferable to use the polymerizablecomposition that includes the initiator (particularly a photoinitiator)in order to implement more efficient polymerization.

Specifically, it is preferable to produce the polymer according to oneembodiment of the invention using the method (B) that applies thepolymerizable composition according to one embodiment of the inventionto a substrate, and polymerizes the applied polymerizable composition.Examples of the substrate include a substrate used to produce anoptically anisotropic article (described later), and the like.

The polymerizable composition according to one embodiment of theinvention may be applied to the substrate using a known coating method(e.g., bar coating method, spin coating method, roll coating method,gravure coating method, spray coating method, die coating method, capcoating method, or dipping method). A known organic solvent may be addedto the polymerizable composition according to one embodiment of theinvention in order to improve the applicability of the polymerizablecomposition. In this case, it is preferable to remove the organicsolvent by natural drying, drying by heating, drying under reducedpressure, drying by heating under reduced pressure, or the like afterapplying the polymerizable composition to the substrate.

The polymerizable compound according to one embodiment of the inventionor the polymerizable composition according to one embodiment of theinvention may be polymerized by applying activated energy rays, orutilizing a thermal polymerization method, for example. It is preferableto polymerize the polymerizable compound or the polymerizablecomposition by applying activated energy rays since heating isunnecessary (i.e., the reaction can be effected at room temperature). Itis preferable to apply light (e.g., ultraviolet rays) to thepolymerizable compound or the polymerizable composition from theviewpoint of convenience.

The temperature during application is preferably set to 30° C. or less.The dose is normally 1 W/m² to 10 kW/m², and preferably 5 W/m² to 2kW/m².

A polymer obtained by polymerizing the polymerizable compound accordingto one embodiment of the invention or the polymerizable compositionaccording to one embodiment of the invention may be removed from thesubstrate, and used alone, or may be used directly as an optical filmorganic material or the like without removing the polymer from thesubstrate.

The number average molecular weight of the polymer according to oneembodiment of the invention thus obtained is preferably 500 to 500,000,and more preferably 5000 to 300,000. When the number average molecularweight of the polymer is within the above range, the resulting filmexhibits high hardness and an excellent handling capability. The numberaverage molecular weight of the polymer may be determined by gelpermeation chromatography (GPC) using monodisperse polystyrene as astandard (eluant: tetrahydrofuran).

It is considered that the polymer according to one embodiment of theinvention has a structure in which crosslinking points are uniformlypresent within the molecule, and exhibits a high crosslinking efficiencyand excellent hardness.

The polymer according to one embodiment of the invention makes itpossible to inexpensively produce an optical film that achieves uniformconversion of polarized light over a wide wavelength band, and exhibitssatisfactory performance.

4) Optically Anisotropic Article

An optically anisotropic article according to one embodiment of theinvention includes the polymer according to one embodiment of theinvention.

The optically anisotropic article according to one embodiment of theinvention may be obtained by forming an alignment film on a substrate,and forming a liquid crystal layer on the alignment film using thepolymer according to one embodiment of the invention.

The alignment film is formed on the surface of the substrate in order toachieve in-plane alignment of an organic semiconductor compound in onedirection.

The alignment film may be obtained by applying a solution (alignmentfilm composition) that includes a polymer (e.g., polyimide, polyvinylalcohol, polyester, polyallylate, polyamideimide, or polyetherimide) tothe substrate to form a film, drying the film, and subjecting the filmto a rubbing treatment in one direction, for example.

The thickness of the alignment film is preferably 0.001 to 5 μm, andmore preferably 0.001 to 1 μm.

The rubbing treatment may be performed on the alignment film or thesubstrate. The rubbing treatment may be implemented using an arbitrarymethod. For example, the alignment film may be rubbed in a givendirection using a roll around which a cloth or felt formed of syntheticfibers (e.g., nylon) or natural fibers (e.g., cotton) is wound. It ispreferable to wash the alignment film with isopropyl alcohol or the likeafter the rubbing treatment in order to remove fine powder (foreignsubstances) formed during the rubbing treatment to clean the surface ofthe alignment film.

The alignment film may be provided with a function of achieving in-planealignment in one direction by applying polarized UV rays to the surfaceof the alignment film.

The liquid crystal layer may be formed on the alignment film using thepolymer according to one embodiment of the invention by utilizing themethod described above in connection with the polymer according to oneembodiment of the invention.

Since the optically anisotropic article according to one embodiment ofthe invention is produced using the polymer according to one embodimentof the invention, the optically anisotropic article can be produced atlow cost, exhibits low reflected luminance, achieves uniform conversionof polarized light over a wide wavelength band, and shows satisfactoryperformance.

Examples of the optically anisotropic article according to oneembodiment of the invention include a retardation film, an alignmentfilm for liquid crystal display elements (liquid crystal displays), apolarizer, a viewing angle enhancement film, a color filter, a low-passfilter, an optical polarization prism, an optical filter, and the like.

5) Carbonyl Compound

A carbonyl compound according to one embodiment of the invention is acompound represented by the formula (4) (hereinafter may be referred toas “carbonyl compound (4)”).

The carbonyl compound (4) according to one embodiment of the inventionmay suitably be used as an intermediate for producing the polymerizablecompound (I) according to one embodiment of the invention. The methodfor producing the carbonyl compound (4) has been described in detailabove in connection with the polymerizable compound (see “1)Polymerizable compound”).

6) Method for Producing Polymerizable Compound, and Method for UsingCarbonyl Compound as Raw Material for Producing Polymerizable Compound

A method for producing a polymerizable compound according to oneembodiment of the invention produces the polymerizable compound (I)according to one embodiment of the invention by reacting the carbonylcompound (4) according to one embodiment of the invention with thehydrazine compound represented by the formula (3). The details of theproduction method have been described above in connection with thepolymerizable compound (see “1) Polymerizable compound”).

The method for producing a polymerizable compound according to oneembodiment of the invention can efficiently and easily produce thepolymerizable compound (1) according to one embodiment of the invention.

A method for using a carbonyl compound as a raw material for producing apolymerizable compound uses the carbonyl compound (4) according to oneembodiment of the invention as a raw material for producing thepolymerizable compound (I) according to one embodiment of the invention.The details of the method have been described above in connection withthe polymerizable compound (see “1) Polymerizable compound”).

It is possible to easily produce the polymerizable compound (I)according to one embodiment of the invention in high yield by utilizingthe carbonyl compound (4) according to one embodiment of the inventionas a raw material.

EXAMPLES

The invention is further described below by way of examples. Note thatthe invention is not limited to the following examples.

Example 1 Synthesis of Compound 1

Step 1: Synthesis of Intermediate A

A three-necked reactor equipped with a thermometer was charged with17.98 g (104.42 mmol) of trans-1,4-cyclohexanedicarboxylic acid and 180ml of tetrahydrofuran (THF) under a nitrogen stream. After the additionof 6.58 g (57.43 mmol) of methanesulfonyl chloride to the mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 20° C. 6.34 g (62.65 mmol) of triethylamine wasadded dropwise to the reaction mixture over 10 minutes while maintainingthe temperature of the reaction mixture at 20 to 30° C. After thedropwise addition, the mixture was stirred at 25° C. for 2 hours.

After the addition of 0.64 g (5.22 mmol) of 4-(dimethylamino)pyridineand 13.80 g (52.21 mmol) of 4-(6-acryloyloxyhex-1-yloxy)phenol(manufactured by DKSH) to the reaction mixture, the reactor was immersedin a water bath to adjust the temperature of the reaction mixture to 15°C. 6.34 g (62.65 mmol) of triethylamine was added dropwise to thereaction mixture over 10 minutes while maintaining the temperature ofthe reaction mixture at 20 to 30° C. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After completion of thereaction, 1000 ml of distilled water and 100 ml of a saturated sodiumchloride solution were added to the reaction mixture, followed byextraction twice with 400 ml of ethyl acetate. The organic layer wascollected, and dried over anhydrous sodium sulfate, and sodium sulfatewas separated by filtration. The solvent was evaporated from thefiltrate using a rotary evaporator, and the residue was purified bysilica gel column chromatography (THF:toluene=1:9 (volume ratio(hereinafter the same)) to obtain 14.11 g of an intermediate A as awhite solid (yield: 65%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.12 (s, 1H), 6.99 (d, 2H, J=9.0Hz), 6.92 (d, 2H, J=9.0 Hz), 6.32 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.17 (dd,1H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz, 10.0 Hz), 4.11 (t, 2H,J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.48-2.56 (m, 1H), 2.18-2.26 (m, 1H),2.04-2.10 (m, 2H), 1.93-2.00 (m, 2H), 1.59-1.75 (m, 4H), 1.35-1.52 (m,8H)

Step 2: Synthesis of Intermediate B

A three-necked reactor equipped with a thermometer was charged with 4.00g (9.56 mmol) of the intermediate A synthesized in the step 1 and 60 mlof THF under a nitrogen stream to prepare a homogeneous solution. Afterthe addition of 1.12 g (9.78 mmol) of methanesulfonyl chloride to thesolution, the reactor was immersed in a water bath to adjust thetemperature of the reaction mixture to 20° C. 1.01 g (9.99 mmol) oftriethylamine was added dropwise to the reaction mixture over 5 minuteswhile maintaining the temperature of the reaction mixture at 20 to 30°C. After the dropwise addition, the mixture was stirred at 25° C. for 2hours. After the addition of 0.11 g (0.87 mmol) of4-(dimethylamino)pyridine and 0.60 g (4.35 mmol) of2,5-dihydroxybenzaldehyde to the reaction mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 1.10 g (10.87 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 400 ml of distilled water and 50 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 750 ml of ethyl acetate. The organiclayer was collected, and dried over anhydrous sodium sulfate, and sodiumsulfate was separated by filtration. The solvent was evaporated from thefiltrate using a rotary evaporator, and the residue was dissolved in 100ml of THF. 500 ml of methanol was added to the solution to precipitatecrystals, which were filtered off. The crystals were washed withmethanol, and dried under vacuum to obtain 2.51 g of an intermediate Bas a white solid (yield: 62%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.02 (s, 1H), 7.67 (d, 1H, J=3.0Hz), 7.55 (dd, 1H, J=3.0 Hz, 8.5 Hz), 7.38 (d, 1H, J=8.5 Hz), 6.99-7.04(m, 4H), 6.91-6.96 (m, 4H), 6.32 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.17 (dd,2H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 2H, J=1.5 Hz, 10.0 Hz), 4.11 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.56-2.81 (m, 4H), 2.10-2.26 (m, 8H),1.50-1.76 (m, 16H), 1.33-1.49 (m, 8H)

Step 3: Synthesis of Compound 1

A three-necked reactor equipped with a thermometer was charged with 2.30g (2.45 mmol) of the intermediate B synthesized in the step 2 and 25 mlof THF under a nitrogen stream to prepare a homogeneous solution. 0.49ml (0.25 mmol) of concentrated hydrochloric acid was added to thesolution. A solution prepared by dissolving 0.40 g (2.45 mol) of2-hydrazinobenzothiazole in 5 ml of THF was added dropwise to thesolution over 15 minutes. After the dropwise addition, the mixture wasstirred at 25° C. for 1 hour. After completion of the reaction, thereaction mixture was added to 400 ml of methanol to precipitate a solid,which was filtered off. The solid was dried using a vacuum dryer toobtain 2.4 g of a compound 1 as a light yellow solid (yield: 90%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.63 (s, 1H), 8.10 (s, 1H), 7.80(d, 1H, J=5.0 Hz), 7.60 (d, 1H, J=3.0 Hz), 7.48 (s, 1H), 7.21-7.35 (m,3H), 7.14 (t, 1H, J=7.5 Hz), 6.98-7.05 (m, 4H), 6.91-6.97 (m, 4H), 6.32(dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.0 Hz, 17.5 Hz), 5.93(dd, 2H, J=1.5 Hz, 10.0 Hz), 4.12 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.83 (m, 4H), 2.11-2.30 (m, 8H), 1.52-1.80 (m, 16H), 1.33-1.49(m, 8H)

Example 2 Synthesis of Compound 2

Step 1: Synthesis of Intermediate C

A three-necked reactor equipped with a thermometer was charged with 9.00g (70.01 mmol) of 3-amino-2-chloropyridine and 90 ml of concentratedhydrochloric acid under a nitrogen stream to prepare a homogeneoussolution. After the addition of 10.21 g (105.01 mmol) of potassiumthiocyanate to the solution, the mixture was stirred at 100° C. for 4hours. After completion of the reaction, the reaction mixture was cooledto 20° C., followed by addition of 90 ml of water. The reaction mixturewas added to 300 ml of a saturated sodium hydrogen carbonate aqueoussolution while cooling the mixture with ice. The pH of the aqueoussolution was adjusted to 8 by adding powdery sodium carbonate toprecipitate crystals. The crystals were filtered off, washed withdistilled water, and dried using a vacuum dryer to obtain 8.74 g of anintermediate C as a light yellow solid (yield: 83%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.11 (dd, 1H, J=1.5 Hz, 5.0 Hz),7.82 (s, 2H), 7.63 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.25 (dd, 1H, J=5.0 Hz,8.0 Hz)

Step 2: Synthesis of Intermediate D

CH₃CH₂CH₂CH₂CH₂CH₂—NHNH₂   Intermediate D

A three-necked reactor equipped with a thermometer was charged with182.0 g (3635 mol) of hydrazine monohydrate, followed by heating to 40°C. under a nitrogen stream. A solution prepared by mixing 60.0 g (363.5mmol) of 1-bromohexane and 60 ml of ethanol was added dropwise to thereactor over 4 hours using a dropping funnel. After the dropwiseaddition, the mixture was stirred at 40° C. for 1 hour. After coolingthe reaction mixture to 25° C., 200 ml of distilled water was added tothe reaction mixture, followed by extraction twice with 300 ml ofchloroform. The organic layer was collected, and dried over anhydroussodium sulfate, and sodium sulfate was separated by filtration. Thefiltrate was concentrated using a rotary evaporator, and the concentratewas distilled under reduced pressure to obtain 10.44 g of anintermediate D as a colorless transparent liquid (degree of vacuum: 3.0kPa, boiling point: 90° C.) (yield: 25%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 3.02 (s, 3H), 2.76 (t, 2H, J=7.0Hz), 1.44-1.53 (m, 2H), 1.24-1.37 (m, 6H), 0.89 (t, 3H, J=7.0 Hz)

Step 3: Synthesis of Intermediate E

A three-necked reactor equipped with a thermometer was charged with 2.70g (17.86 mmol) of the intermediate C synthesized in the step 1, 10.38 g(89.29 mmol) of the intermediate D synthesized in the step 2, 1.49 ml(17.86 mmol) of concentrated hydrochloric acid, and 25 ml of ethyleneglycol under a nitrogen stream to prepare a homogenous solution. Thesolution was stirred at 140° C. for 20 hours. After completion of thereaction, the reaction mixture was cooled to 20° C. 300 ml of distilledwater and 50 ml of a saturated sodium chloride solution were added tothe reaction mixture, followed by extraction with 500 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (THF:toluene=1:9) to obtain 1.33 gof an intermediate E as a light yellow solid (yield: 30%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.07 (dd, 1H, J=1.5 Hz, 5.0 Hz),7.62 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.22 (dd, 1H, J=5.0 Hz, 8.0 Hz), 5.46(s, 2H), 3.70 (t, 2H, J=7.0 Hz), 1.64-1.73 (m, 2H), 1.22-1.35 (m, 6H),0.86 (t, 3H, J=7.0 Hz)

Step 4: Synthesis of Compound 2

A three-necked reactor equipped with a thermometer was charged with 1.20g (1.28 mmol) of the intermediate B synthesized in the step 2 of Example1 and 30 ml of THF under a nitrogen stream to prepare a homogeneoussolution. After the addition of 0.26 ml (0.26 mmol) of 1 N hydrochloricacid, a solution prepared by dissolving 0.48 g (1.92 mmol) of theintermediate E synthesized in the step 3 in 5 ml of THF was addeddropwise to the mixture over 15 minutes. After the dropwise addition,the mixture was stirred at 25° C. for 5 hours. 250 ml of methanol wasadded to the reaction mixture to precipitate a solid, which was filteredoff. The solid was purified by silica gel column chromatography(chloroform:THF=97:3) to obtain 1.25 g of a compound 2 as a light yellowsolid (yield: 84%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.30 (dd, 1H, J=1.5 Hz, 5.0 Hz),7.96 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.89 (s, 1H), 7.63 (d, 1H, J=3.0 Hz),7.39 (dd, 1H, J=5.0 Hz, 8.0 Hz), 7.32 (d, 1H, J=8.5 Hz), 7.27 (dd, 1H,J=3.0 Hz, 8.5 Hz), 6.98-7.04 (m, 4H), 6.91-6.97 (m, 4H), 6.32 (dd, 2H,J=1.5 Hz, 17.5 Hz), 6.17 (dd, 2H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 2H,J=1.5 Hz, 10.0 Hz), 4.35 (t, 2H, J=7.0 Hz), 4.11 (t, 4H, J=6.5 Hz), 3.95(t, 4H, J=6.5 Hz), 2.56-2.84 (m, 4H), 2.11-2.30 (m, 8H), 1.52-1.75 (m,18H), 1.22-1.49 (m, 14H), 0.85 (t, 3H, J=7.0 Hz)

Example 3 Synthesis of Compound 3

Step 1: Synthesis of Intermediate F

A four-necked reactor equipped with a thermometer was charged with 20.0g (125 mmol) of 1,4-dihydroxynaphthalene and 200 ml ofN,N-dimethylformamide (DMF) under a nitrogen stream to prepare ahomogeneous solution. After the addition of 51.8 g (375 mmol) ofpotassium carbonate and 19.4 ml (312 mmol) of methyl iodide to thesolution, the mixture was stirred at 25° C. for 20 hours. Aftercompletion of the reaction, the reaction mixture was filtered throughcelite. The filtrate was added to 500 ml of water, and extracted with500 ml of ethyl acetate. The ethyl acetate layer was dried overanhydrous sodium sulfate, and sodium sulfate was separated byfiltration. Ethyl acetate was evaporated from the filtrate under reducedpressure using a rotary evaporator to obtain a white solid. The whitesolid was recrystallized from n-hexane (125 ml) to obtain 20.3 g of anintermediate F as colorless crystals (yield: 86.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.19-8.22 (m, 2H), 7.52-7.48 (m,2H), 6.69 (s, 2H), 3.95 (s, 6H)

Step 2: Synthesis of Intermediate G

A four-necked reactor equipped with a thermometer was charged with 15.0g (79.7 mmol) of the intermediate F synthesized in the step 1 and 100 mlof dichloromethane under a nitrogen stream to prepare a homogeneoussolution. After the addition of 91.7 g (91.7 mmol) of titaniumtetrachloride (1.0 M dichloromethane solution) and 8.11 ml (91.7 mmol)of dichloromethyl methyl ether dropwise to the solution, the mixture wasstirred at 0° C. for 1 hour. After completion of the reaction, thereaction mixture was added to 300 ml of ice water, and extracted with500 ml of ethyl acetate. After drying the ethyl acetate layer overanhydrous magnesium sulfate, magnesium sulfate was separated byfiltration. Ethyl acetate was evaporated from the filtrate under reducedpressure using a rotary evaporator to obtain a white solid. The whitesolid was recrystallized from n-hexane (260 ml) to obtain 16.6 g of anintermediate G as colorless crystals (yield: 96.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.58 (s, 1H), 8.28-8.31 (m, 1H),8.20-8.22 (m, 1H), 7.61-7.67 (m, 2H), 7.13 (s, 1H), 4.10 (s, 3H), 4.03(s, 3H)

Step 3: Synthesis of Intermediate H

A four-necked reactor equipped with a thermometer was charged with 16.6g (76.8 mmol) of the intermediate G synthesized in the step 2 and 100 mlof dichloromethane under a nitrogen stream to prepare a homogeneoussolution. The solution was cooled to −40° C. After the addition of 230ml (230 mmol) of boron tribromide (17% dichloromethane solution)dropwise to the solution, the mixture was heated to 25° C., and stirredfor 2 hours. After completion of the reaction, the reaction mixture wasadded to 500 ml of ice water, and extracted with 500 ml ofdichloromethane. After drying the dichloromethane layer over anhydrousmagnesium sulfate, magnesium sulfate was separated by filtration.Dichloromethane was evaporated from the filtrate under reduced pressureusing a rotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (n-hexane:ethylacetate=70:30) to obtain 12.7 g of an intermediate H as a yellow solid(yield: 87.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 M Hz, CDCl₃, TMS, δ ppm): 12.31 (s, 1H), 9.88 (s, 1H), 8.45(d, 1H, J=8.5 Hz), 8.16 (d, 1H, J=8.5 Hz), 7.72 (dd, 1H, J=7.8 Hz, 8.5Hz), 7.61 (dd, 1H, J=7.8 Hz, 8.5 Hz), 6.83 (s, 1H), 5.17 (s, 1H)

Step 4: Synthesis of Intermediate I

A three-necked reactor equipped with a thermometer was charged with 3.19g (7.61 mmol) of the intermediate A synthesized in the step 1 of Example1 and 50 ml of THF under a nitrogen stream to prepare a homogeneoussolution. After the addition of 0.91 g (7.93 mmol) of methanesulfonylchloride to the solution, the reactor was immersed in a water bath toadjust the temperature of the reaction mixture to 20° C. 0.80 g (7.93mmol) of triethylamine was added dropwise to the reaction mixture over 5minutes while maintaining the temperature of the reaction mixture at 20to 30° C. After the dropwise addition, the mixture was stirred at 25° C.for 2 hours. After the addition of 0.08 g (0.63 mmol) of4-(dimethylamino)pyridine and 0.60 g (3.17 mmol) of the intermediate Hsynthesized in the step 3 to the reaction mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 0.80 g (7.93 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes while maintaining the temperatureof the reaction mixture at 20 to 30° C. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. 150 ml of distilled water and50 ml of a saturated sodium chloride solution were added to the reactionmixture, followed by extraction twice with 300 ml of ethyl acetate. Theorganic layer was collected, and dried over anhydrous sodium sulfate,and sodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the resulting solid wasdissolved in 100 ml of THF. 500 ml of methanol was added to the solutionto precipitate crystals, which were filtered off. The crystals werewashed with methanol, and dried under vacuum to obtain 1.82 g of anintermediate I as a grayish white solid (yield; 58%).

The structure of the target product was identified by ¹H-NMR.

1H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.22 (s, 1H), 8.11 (d, 1H, J=8.5Hz), 7.99 (d, 1H, J=8.5 Hz), 7.76-7.91 (m, 2H), 7.71 (s, 1H), 7.01-7.07(m, 4H), 6.91-6.98 (m, 4H), 6.32 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd,2H, J=10.0 Hz, 17.5 Hz), 5.94 (dd, 2H, J=1.5 Hz, 10.0 Hz), 4.12 (t, 4H,J=6.5 Hz), 3.96 (t, 4H, J=6.5 Hz), 3.02-3.12 (m, 1H), 2.86-2.97 (m, 1H),2.60-2.74 (m, 2H), 2.28-2.43 (m, 4H), 2.14-2.27 (m, 4H), 1.54-1.86 (m,16H), 1.30-1.53 (m, 8H)

Step 5: Synthesis of Compound 3

A three-necked reactor equipped with a thermometer was charged with 1.67g (1.69 mmol) of the intermediate I synthesized in the step 4 and 30 mlof THF under a nitrogen stream to prepare a homogeneous solution. Afterthe addition of 0.34 ml (0.34 mmol) of 1 N hydrochloric acid to thesolution, a solution prepared by dissolving 0.85 g (3.38 mol) of theintermediate E synthesized in the step 3 of Example 2 in 5 ml of THF wasadded dropwise to the mixture over 30 minutes. After the dropwiseaddition, the mixture was stirred at 25° C. for 5 hours. The reactionmixture was added to 250 ml of methanol to precipitate a solid, whichwas filtered off. The solid was purified by silica gel columnchromatography (chloroform:THF=97:3) to obtain 1.61 g of a compound 3 asa light yellow solid (yield: 78%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.31 (dd, 1H, J=1.5 Hz, 5.0 Hz),7.94-7.99 (m, 2H), 7.88-7.94 (m, 2H), 7.78 (s, 1H), 7.69-7.76 (m, 2H),7.40 (dd, 1H, J=5.0 Hz, 8.0 Hz), 6.99-7.08 (m, 4H), 6.90-6.98 (m, 4H),6.32 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.0 Hz, 17.5 Hz),5.94 (dd, 2H, J=1.5 Hz, 10.0 Hz), 4.40 (t, 2H, J=7.0 Hz), 4.12 (t, 4H,J=6.5 Hz), 3.96 (t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz), 2.89-3.12 (m,2H), 2.61-2.75 (m, 2H), 2.30-2.42 (m, 4H), 2.15-2.28 (m, 4H), 1.55-1.85(m, 18H), 1.19-1.52 (m, 14H), 0.86 (t, 3H, J=7.0 Hz)

Example 4 Synthesis of Compound 4

Step 1: Synthesis of Intermediate J

A four-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 20 ml of DMF under anitrogen stream to prepare a homogeneous solution. After the addition of8.36 g (60.5 mmol) of potassium carbonate and 3.08 g (14.5 mmol) of1-iodohexane to the solution, the mixture was stirred at 50° C. for 7hours. After completion of the reaction, the reaction mixture was cooledto 20° C., added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (hexane:ethyl acetate=75:25) to obtain2.10 g of an intermediate J as a white solid (yield: 69.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.53 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0 Hz), 4.22 (s, 2H), 3.74 (t,2H, J=7.5 Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0.89 (t, 3H, J=7.0Hz)

Step 2: Synthesis of Compound 4

A four-necked reactor equipped with a thermometer was charged with 697mg (2.37 mmol) of the intermediate J synthesized in the step 1, 2.00 g(2.13 mmol) of the intermediate B synthesized in Example 1, 3 ml ofethanol, and 20 ml of THF under a nitrogen stream to prepare ahomogeneous solution. After the addition of 55.1 mg (0.24 mmol) of(±)-10-camphorsulfonic acid to the solution, the mixture was stirred at40° C. for 5 hours. After completion of the reaction, the reactionmixture was added to 150 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a white solid. The white solid was purified bysilica gel column chromatography (toluene:ethyl acetate=90:10) to obtain2.24 g of a compound 4 as a white solid (yield: 86.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=2.5 Hz), 7.67-7.70(m, 3H), 7.34 (ddd, 1H, J=1.0 Hz, 7.0 Hz, 7.5 Hz), 7.17 (ddd, 1H, J=1.0Hz, 7.5 Hz, 7.5 Hz), 7.12 (d, 1H, J=9.0 Hz), 7.10 (dd, 1H, J=2.5 Hz, 9.0Hz), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J=8.0 Hz), 4.18 (t,4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.58-2.70 (m, 4H), 2.31-2.35 (m,8H), 1.66-1.82 (m, 18H), 1.31-1.54 (m, 14H), 0.90 (t, 3H, J=7.0 Hz)

Example 5 Synthesis of Compound 5

Step 1: Synthesis of Intermediate K

A four-necked reactor equipped with a thermometer was charged with 1.50g (6.48 mmol) of 2-(methylthio)naphtho[1,2d]thiazole and 15 ml ofmethylene chloride under a nitrogen stream to prepare a homogeneoussolution. After the addition of 3.52 g (14.3 mmol) of 3-chloroperbenzoicacid (water content: about 30%) to the solution, the mixture was stirredat 25° C. for 8 hours. After completion of the reaction, the reactionmixture was added to 100 ml of saturated sodium bicarbonate water, andextracted twice with 200 ml of methylene chloride. After drying themethylene chloride layer over anhydrous magnesium sulfate, magnesiumsulfate was separated by filtration. Methylene chloride was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a white solid. The white solid was purified by silica gel columnchromatography (toluene:ethyl acetate=90:10) to obtain 1.49 g of anintermediate K as a white solid (yield: 74.6%).

The structure of the target product was identified by ¹H-NMR and¹³C-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 8.84 (d, 1H, J=7.6 Hz), 8.00 (d,1H, J=8.0 Hz), 7.99 (d, 1H, J=9.2 Hz), 7.95 (d, 1H, J=9.2 Hz), 7.75 (dd,1H, J=7.6 Hz, 8.0 Hz), 7.68 (dd, 1H, J=7.6 Hz, 7.6 Hz), 3.48 (s, 3H)

¹³C-NMR (100 MHz, CDCl₃, TMS, δ ppm): 164.6, 149.7, 134.7, 132.3, 129.5,129.2, 128.4, 128.1, 127.5, 124.0, 118.7, 42.8

Step 2: Synthesis of Intermediate L

A four-necked reactor equipped with a thermometer was charged with 1.49g (4.83 mmol) of the intermediate K synthesized by the step 1, 1.2 ml(24.2 mmol) of hydrazine monohydrate, 10 ml of 1-propanol, and 5 ml ofTHF under a nitrogen stream to prepare a homogenous solution. Thesolution was stirred at 80° C. for 4 hours. After completion of thereaction, the reaction mixture was cooled to 20° C., followed byaddition of 20 ml of water to precipitate a solid, which was filteredoff. The solid was washed with water, and dried using a vacuum dryer toobtain 993 mg of an intermediate L as a light yellow solid (yield:95.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 9.20 (s, 1H), 8.34 (d, 1H, J=8.0Hz), 7.90 (d, 1H, J=8.0 Hz), 7.83 (d, 1H, J=8.5 Hz), 7.53 (d, 1H, J=8.5Hz), 7.51 (dd, 1H, J=7.5 Hz, 8.0 Hz), 7.46 (dd, 1H, J=7.5 Hz, 8.0 Hz),5.12 (s, 2H)

Step 3: Synthesis of Intermediate M

A four-necked reactor equipped with a thermometer was charged with 993mg (4.61 mmol) of the intermediate L synthesized in the step 2 and 10 mlof DMF under a nitrogen stream to prepare a homogeneous solution. Afterthe addition of 3.00 g (9.22 mmol) of cesium carbonate and 1.17 g (5.53mmol) of 1-iodohexane to the solution, the mixture was stirred at 25° C.for 5 hours. After completion of the reaction, the reaction mixture wasadded to 100 ml of water, and extracted with 300 ml of ethyl acetate.After drying the ethyl acetate layer over anhydrous sodium sulfate,sodium sulfate was separated by filtration. Ethyl acetate was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a light yellow solid. The yellow solid was purified by silica gelcolumn chromatography (hexane:ethyl acetate=90:10) to obtain 545 mg ofan intermediate M as a white solid (yield: 39.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.57 (d, 1H, J=8.0 Hz), 7.85 (d,1H, J=8.0 Hz), 7.69 (d, 1H, J=8.5 Hz), 7.532 (d, 1H, J=8.5 Hz), 7.531(dd, 1H, J=7.5 Hz, 8.0 Hz), 7.46 (dd, 1H, J=7.5 Hz, 8.0 Hz), 4.27 (s,2H), 3.83 (t, 2H, J=7.5 Hz), 1.76 (tt, 2H, J=7.5 Hz, 7.5 Hz), 1.34-1.45(m, 6H), 0.90 (t, 3H, J=7.0 Hz)

Step 4: Synthesis of Intermediate N

A four-necked reactor equipped with a thermometer was charged with 545mg (1.82 mmol) of 2,5-dihydroxybenzaldehyde, 1.40 g (1.40 mmol) of theintermediate M synthesized in the step 3, and 10 ml of 1-propanol undera nitrogen stream to prepare a homogenous solution. After the additionof 42.3 mg (0.18 mmol) of (±)-10-camphorsulfonic acid to the solution,the mixture was stirred at 25° C. for 4 hours. After completion of thereaction, 100 ml of water was added to the mixture to precipitate asolid, which was filtered off. The solid was washed with water, anddried using a vacuum dryer to obtain 588 mg of an intermediate N as ayellow solid (yield: 76.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 9.42 (s, 1H), 8.99 (s, 1H), 8.51(d, 1H, J=8.0 Hz), 8.19 (s, 1H), 7.98 (d, 1H, J=8.0 Hz), 7.96 (d, 1H,J=8.5 Hz), 7.70 (d, 1H, J=8.5 Hz), 7.61 (dd, 1H, J=7.5 Hz, 8.0 Hz), 7.54(dd, 1H, J=7.5 Hz, 8.0 Hz), 7.22 (d, 1H, J=3.0 Hz), 6.78 (d, 1H, J=9.0Hz), 6.71 (dd, 1H, J=3.0 Hz, 9.0 Hz), 4.47 (t, 2H, J=7.0 Hz), 1.75 (tt,2H, J=7.0 Hz, 7.0 Hz), 1.38-1.46 (m, 4H), 1.26-1.33 (m, 2H), 0.86 (t,3H, J=7.5 Hz)

Step 5: Synthesis of Compound 5

A four-necked reactor equipped with a thermometer was charged with 588mg (1.40 mmol) of the intermediate N synthesized in the step 4, 1.47 g(3.50 mmol) of the intermediate A synthesized in Example 1, 85.5 mg(0.70 mmol) of 4-(dimethylamino)pyridine, and 15 ml ofN-methylpyrrolidone under a nitrogen stream to prepare a homogeneoussolution. After the addition of 805 mg (4.20 mmol) of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) to thesolution, the mixture was stirred at 25° C. for 5 hours. Aftercompletion of the reaction, the reaction mixture was added to 150 ml ofwater, and extracted with 300 ml of ethyl acetate. After drying theethyl acetate layer over anhydrous sodium sulfate, sodium sulfate wasseparated by filtration. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a whitesolid. The white solid was purified by silica gel column chromatography(toluene:ethyl acetate=90:10) to obtain 1.12 g of a compound 5 as awhite solid (yield: 65.5%).

The structure of the target product was identified by ¹H-NMR.

1H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.63 (d, 1H, J=8.0 Hz), 7.89 (d,1H, J=8.0 Hz), 7.78 (d, 1H, J=2.5 Hz), 7.76 (d, 1H, J=8.5 Hz), 7.63 (d,1H, J=8.5 Hz), 7.58 (dd, 1H, J=7.5 Hz, 8.0 Hz), 7.50 (dd, 1H, J=7.5 Hz,8.0 Hz), 7.13 (d, 1H, J=9.0 Hz), 7.10 (dd, 1H, J=2.5 Hz, 9.0 Hz), 6.99(d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.40(dd, 2H, J=1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.0 Hz), 5.82(dd, 2H, J=1.5 Hz, 10.5 Hz), 4.42 (t, 2H, J=7.5 Hz), 4.17 (t, 4H, J=6.5Hz), 3.94 (t, 4H, J=6.0 Hz), 3.47 (d, 1H, J=4.5 Hz), 2.57-2.71 (m, 4H),2.30-2.35 (m, 8H), 1.76-1.82 (m, 6H), 1.66-1.74 (m, 12H), 1.32-1.54 (m,14H), 0.92 (t, 3H, J=7.5 Hz)

Example 6 Synthesis of Compound 6

Step 1: Synthesis of Intermediate O

A four-necked reactor equipped with a thermometer was charged with 3.46g (26.7 mmol) of 2-amino-3-chloropyrazine, 8.56 g (53.4 mmol) ofpotassium ethylxanthate, and 30 ml of DMF under a nitrogen stream toprepare a homogeneous solution. The solution was refluxed with heatingfor 7 hours, and the reaction mixture was cooled to 0° C. After theaddition of 3.3 ml (53.4 mmol) of methyl iodide, the mixture was stirredat 0° C. for 1 hour. After completion of the reaction, the reactionmixture was added to 300 ml of water, and extracted with 500 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (toluene:ethyl acetate=90:10) to obtain4.38 g of an intermediate O as a light yellow solid (yield: 89.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.55 (d, 1H, J=2.5 Hz), 8.37 (d,1H, J=2.5 Hz), 2.88 (s, 3H)

¹³C-NMR (125 MHz, CDCl₃, TMS, δ ppm): 175.2, 158.0, 153.3, 141.7, 139.4,15.4

Step 2: Synthesis of Intermediate P

A four-necked reactor equipped with a thermometer was charged with 1.50g (8.19 mmol) of the intermediate O synthesized in the step 1, 4.0 ml(81.9 mmol) of hydrazine monohydrate, and 10 ml of ethanol under anitrogen stream to prepare a homogenous solution. The solution wasstirred at 25° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water to precipitate a solid,which was filtered off. The solid was washed with water, and dried usinga vacuum dryer to obtain 1.15 g of an intermediate P as a yellow solid(yield: 84.0%).

The structure of the target product was identified by ¹H-NMR and¹³C-NMR.

¹H-NMR (400 MHz, DMSO-d₆, TMS, δ ppm): 9.99 (brs, 1H), 8.17 (d, 1H,J=2.6 Hz), 7.97 (d, 1H, J=2.6 Hz), 5.30 (s, 2H)

¹³C-NMR (100 MHz, DMSO-d₆, TMS, δ ppm): 175.5, 160.4, 150.8, 140.7,135.3

Step 3: Synthesis of Compound 6

A four-necked reactor equipped with a thermometer was charged with 390mg (2.34 mmol) of the intermediate P synthesized in the step 2, 2.08 mg(2.22 mmol) of the intermediate B synthesized in Example 1, 3 ml ofethanol, and 15 ml of THF under a nitrogen stream to prepare ahomogeneous solution. After the addition of 54.4 mg (0.23 mmol) of(±)-10-camphorsulfonic acid to the solution, the mixture was stirred at40° C. for 5 hours. After completion of the reaction, the reactionmixture was added to 150 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a light yellow solid. The light yellow solid waspurified by silica gel column chromatography (chloroform:methanol=95:5)to obtain 1.82 g of a compound 6 as a light yellow solid (yield: 75.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 13.00 (brs, 1H), 8.84 (s, 1H), 8.33(d, 1H, J=2.5 Hz), 8.22 (d, 1H, J=2.5 Hz), 7.71 (d, 1H, J=2.5 Hz), 7.19(dd, 1H, J=2.5 Hz, 9.0 Hz), 7.14 (d, 1H, J=9.0 Hz), 6.99 (d, 2H, J=9.0Hz), 6.96 (d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz), 6.86 (d, 2H, J=9.0Hz), 6.403 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.398 (dd, 1H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.12 (dd, 1H, J=10.5 Hz, 17.5Hz), 5.822 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.817 (dd, 1H, J=1.5 Hz, 10.5Hz), 4.18 (t, 2H, J=7.0 Hz), 4.17 (t, 2H, J=7.0 Hz), 3.95 (t, 2H, J=6.5Hz), 3.93 (t, 2H, J=6.5 Hz), 2.59-2.66 (m, 3H), 2.46-2.52 (m, 1H),2.17-2.34 (m, 8H), 1.41-1.82 (m, 24H)

Example 7 Synthesis of Compound 7

Step 1: Synthesis of Intermediate Q

A four-necked reactor equipped with a thermometer was charged with 4.17g (24.9 mmol) of the intermediate P synthesized in the step 2 of Example6 and 30 ml of DMF under a nitrogen stream to prepare a homogeneoussolution. After the addition of 16.2 g (49.8 mmol) of cesium carbonateand 4.4 ml (29.9 mmol) of 1-iodohexane to the solution, the mixture wasstirred at 25° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 200 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a white solid. The white solid was purifiedby silica gel column chromatography (toluene:ethyl acetate=60:40) toobtain 1.69 g of an intermediate Q as a white solid (yield: 27.0%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.22 (d, 1H, J=3.0 Hz), 8.02 (d,1H, J=3.0 Hz), 5.65 (s, 2H), 3.78 (t, 2H, J=7.0 Hz), 1.71 (tt, 2H, J=7.0Hz, 7.0 Hz), 1.26-1.32 (m, 6H), 0.86 (t, 3H, J=7.0 Hz)

Step 2: Synthesis of Compound 7

A four-necked reactor equipped with a thermometer was charged with 338mg (1.34 mmol) of the intermediate Q synthesized in the step 1, 1.20 g(1.28 mmol) of the intermediate B synthesized in Example 1, 3 ml ofethanol, and 10 ml of THF under a nitrogen stream to prepare ahomogeneous solution. After the addition of 15.6 mg (0.13 mmol) of(±)-10-camphorsulfonic acid to the solution, the mixture was stirred at40° C. for 5 hours. After completion of the reaction, the reactionmixture was added to 100 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a white solid. The white solid was purified bysilica gel column chromatography (toluene:ethyl acetate=90:10) to obtain1.21 g of a compound 7 as a white solid (yield: 79.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.39 (d, 1H, J=2.5 Hz), 8.20 (d,1H, J=2.5 Hz), 7.84 (s, 1H), 7.75 (d, 1H, J=2.0 Hz), 7.14-7.18 (m, 2H),6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz),6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz),5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.36 (t, 2H, J=7.5 Hz), 4.18 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.56-2.72 (m, 4H), 2.25-2.36 (m, 8H),1.69-1.83 (m, 18H), 1.41-1.54 (m, 10H), 1.30-1.39 (m, 4H), 0.90 (t, 3H,J=7.0 Hz)

Example 8 Synthesis of Compound 8

Step 1: Synthesis of Intermediate R

A four-necked reactor equipped with a thermometer was charged with 8.89g (56.4 mmol) of 4-amino-5-chloro-2,6-dimethylpyrimidine, 18.1 g (113mmol) of potassium ethylxanthate, and 100 ml of DMF under a nitrogenstream to prepare a solution. The solution was refluxed with heating for8 hours, and the reaction mixture was cooled to 0° C. After the additionof 7.0 ml (113 mmol) of methyl iodide, the mixture was stirred at 0° C.for 1 hour. After completion of the reaction, the reaction mixture wasadded to 500 ml of water, and extracted with 700 ml of ethyl acetate.After drying the ethyl acetate layer over anhydrous sodium sulfate,sodium sulfate was separated by filtration. Ethyl acetate was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a yellow solid. The yellow solid was purified by silica gelcolumn chromatography (toluene:ethyl acetate=80:20) to obtain 6.88 g ofan intermediate R as a light yellow solid (yield: 57.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 2.83 (s, 3H), 2.79 (s, 3H), 2.67(s, 3H)

Step 2: Synthesis of Intermediate S

A four-necked reactor equipped with a thermometer was charged with 4.54g (21.5 mmol) of the intermediate R synthesized in the step 1, 10.0 ml(215 mmol) of hydrazine monohydrate, and 80 ml of ethanol under anitrogen stream to prepare a solution. The solution was stirred at 25°C. for 2 hours. After completion of the reaction, the reaction mixturewas added to 300 ml of water to precipitate a solid, which was filteredoff. The solid was washed with water, and dried using a vacuum dryer toobtain 4.12 g of an intermediate S as a light yellow solid (yield:98.1%).

The structure of the target product was identified by ¹H-NMR and¹³C-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.08 (s, 1H), 5.36 (s, 2H), 2.48(s, 3H), 2.45 (s, 3H)

¹³C-NMR (125 MHz, DMSO-d₆, TMS, δ ppm): 178.2, 170.9, 167.8, 156.3,118.0, 25.3, 23.2

Step 3: Synthesis of Compound 8

A four-necked reactor equipped with a thermometer was charged with 460mg (2.36 mmol) of the intermediate S synthesized in the step 2, 2.00 g(2.12 mmol) of the intermediate B synthesized in Example 1, 3 ml ofethanol, and 20 ml of THF under a nitrogen stream to prepare a solution.After the addition of 54.8 mg (0.24 mmol) of (±)-10-camphorsulfonic acidto the solution, the mixture was stirred at 40° C. for 3 hours. Aftercompletion of the reaction, the reaction mixture was added to 150 ml ofwater, and extracted with 300 ml of ethyl acetate, After drying theethyl acetate layer over anhydrous sodium sulfate, sodium sulfate wasseparated by filtration. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a yellowsolid. The yellow solid was purified by silica gel column chromatography(toluene:ethyl acetate=90:10) to obtain 1.02 g of a compound 8 as ayellow solid (yield: 43.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 13.51 (brs, 1H), 8.85 (s, 1H), 7.72(d, 1H, J=2.5 Hz), 7.18 (dd, 1H, J=2.5 Hz, 8.8 Hz), 7.13 (d, 1H, J=8.8Hz), 6.98 (d, 2H, J=9.0 Hz), 6.95 (d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0Hz), 6.87 (d, 2H, J=9.0 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.40 (dd,1H, J=1.5 Hz, 17.5 Hz), 6.14 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.11 (dd, 1H,J=10.5 Hz, 17.5 Hz), 5.83 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=7.5 Hz), 4.17 (t, 2H, J=7.0 Hz), 3.95(t, 2H, J=6.5 Hz), 3.93 (t, 2H, J=6.5 Hz), 2.75 (s, 3H), 2.62 (s, 3H),2.58-2.60 (m, 2H), 2.38-2.51 (m, 2H), 2.26-2.34 (m, 4H), 2.07-2.14 (m,4H), 1.63-1.82 (m, 10H), 1.41-1.53 (m, 14H)

Synthesis Example 1 Synthesis of Compound A

Step 1: Synthesis of Intermediate A

A four-necked reactor equipped with a thermometer was charged with 20 g(144.8 mmol) of 2,5-dihydroxybenzaldehyde, 105.8 g (362.0 mmol) of4-(6-acryloylhex-1-yloxy)benzoic acid (manufactured by DKSH Japan K.K.),5.3 g (43.4 mmol) of 4-(dimethylamino)pyridine, and 200 ml ofN-methylpyrrolidone under a nitrogen stream to prepare a homogeneoussolution. After the addition of 83.3 g (434.4 mmol) of1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC), themixture was stirred at 25° C. for 12 hours. After completion of thereaction, the reaction mixture was added to 1.5 l of water, andextracted with 500 ml of ethyl acetate. The ethyl acetate layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. Ethyl acetate was evaporated from the filtrate under reducedpressure using a rotary evaporator to obtain a light yellow solid. Thelight yellow solid was purified by silica gel column chromatography(toluene:ethyl acetate=9:1) to obtain 75 g of an intermediate a as awhite solid (yield: 75.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 10.20 (s, 1H), 8.18-8.12 (m, 4H),7.78 (d, 1H, J=2.8 Hz), 7.52 (dd, 1H, J=2.8 Hz, 8.7 Hz), 7.38 (d, 1H,J=8.7 Hz), 7.00-6.96 (m, 4H), 6.40 (dd, 2H, J=1.4 Hz, 17.4 Hz), 6.12(dd, 2H, J=10.6 Hz, 17.4 Hz), 5.82 (dd, 2H, J=1.4 Hz, 10.6 Hz), 4.18 (t,4H, J=6.4 Hz), 4.08-4.04 (m, 4H), 1.88-1.81 (m, 4H), 1.76-1.69 (m, 4H),1.58-1.42 (m, 8H)

Step 2: Synthesis of Compound A

A four-necked reactor equipped with a thermometer was charged with 10.5g (15.3 mmol) of the intermediate a and 80 ml of THF under a nitrogenstream to prepare a homogeneous solution. 3.0 g (18.3 mol) of2-hydrazinobenzothiazole was added to the solution to prepare asolution. After the addition of 18 mg (0.08 mmol) of(±)-10-camphorsulfonic acid, the mixture was stirred at 25° C. for 3hours, After completion of the reaction, the reaction mixture was addedto 800 ml of 10% sodium bicarbonate water, and extracted twice with 100ml of ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a light yellow solid. The light yellow solidwas purified by silica gel column chromatography (toluene:ethylacetate=8:2) to obtain 8.0 g of a compound A as a light yellow solid(yield: 62.7%).

The structure of the target product was identified by ¹H-NMR and massspectroscopy.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.30 (br, 1H), 8.19 (s, 1H),8.17-8.12 (m, 4H), 7.76 (d, 1H, J=3.0 Hz), 7.68 (d, 1H, J=7.5 Hz),7.45-7.39 (m, 3H), 7.28 (t, 1H, J=8.0 Hz), 7.18-7.14 (m, 4H), 7.09 (t,1H, J=8.0 Hz), 6.33 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.5Hz, 17.5 Hz), 5.944 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.941 (dd, 1H, J=1.5Hz, 10.5 Hz), 4.14-4.10 (m, 8H), 1.80-1.75 (m, 4H), 1.69-1.63 (m, 4H),1.53-1.38 (m, 8H)

LCMS (APCI) calcd for C₄₆H₄₇N₃O₁₀S: 833 [M+]. Found: 833.

The phase transition temperature was measured by the following methodusing the compounds 1 to 8 obtained in Examples 1 to 8, the compound Aobtained in Synthesis Example 1, the compound 1r of Reference Example 1that was used in Comparative Example 1 (“K35” manufactured by ZeonCorporation), and the compound 2r of Reference Example 2 that was usedin Comparative Example 2 (“LC242” manufactured by BASF).

Phase Transition Temperature Measurement 1

10 mg of each compound (compounds 1 to 8, A, 1r, and 2r) was weighed,and placed in a solid state between two glass substrates provided with apolyimide alignment film subjected to a rubbing treatment (manufacturedby E.H.C. Co. Ltd. (hereinafter the same)). The substrates were placedon a hot plate, heated from 40° C. to 200° C., and cooled to 40° C. Achange in structure when the temperature was changed was observed usinga polarizing microscope (“ECLIPSE LV100 POL” manufactured by NikonCorporation (hereinafter the same)). Note that the phase transitiontemperature of the compounds 4 to 8 was measured within the range of 40°C. to 250° C., and the phase transition temperature of the compound Awas measured within the range of 50° C. to 200° C.

The phase transition temperature measurement results are shown in Table1.

In Table 1, “C” refers to “Crystal”, “N” refers to “Nematic”, and “I”refers to “Isotropic”. The term “Crystal” means that the test compoundwas in a solid phase, the term “Nematic” means that the test compoundwas in a nematic liquid crystal phase, and the term “Isotropic” meansthat the test compound was in an isotropic liquid phase (hereinafter thesame).

TABLE 1 Compound No. Phase transition temperature Example 1 Compound 1 

Example 2 Compound 2 

Example 3 Compound 3 

Example 4 Compound 4 

Example 5 Compound 5 

Example 6 Compound 6 

Example 7 Compound 7 

Example 8 Compound 8 

Synthesis Example 1 Compound A 

Reference Example 1 Compound 1r

Reference Example 2 Compound 2r

Example 9 and Comparative Examples 1 and 2

1 g of each compound (compound 1 obtained in Example 1, compound 1r ofReference Example 1, and compound 2r of Reference Example 2), 30 mg of aphotoinitiator A (“Adekaoptomer N-1919” manufactured by AdekaCorporation (hereinafter the same)), and 100 mg of a 1% cyclopentanonesolution of a surfactant A (“KH-40” manufactured by AGC Seimi ChemicalCo., Ltd. (hereinafter the same)) were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 1, 1r, and 2r).

Examples 10 and 11

1.0 g of the compound 2 obtained in Example 2 or the compound 3 obtainedin Example 3, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 3.0 g ofcyclopentanone and 0.25 g of dimethyl sulfoxide. The solution wasfiltered through a disposable filter having a pore size of 0.45 m toobtain a polymerizable composition (polymerizable compositions 1, 1r,and 2r).

Example 12

0.5 g of the compound 3 obtained in Example 3, 0.5 g of the compound Asynthesized in Synthesis Example 1, 30 mg of the photoinitiator A, and100 mg of a 1% cyclopentanone solution of the surfactant A weredissolved in 2.3 g of cyclopentanone. The solution was filtered througha disposable filter having a pore size of 0.45 μm to obtain apolymerizable composition 4.

Example 13

0.5 g of the compound 3 obtained in Example 3, 0.5 g of the compound 2r,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 2.3 g of cyclopentanone.The solution was filtered through a disposable filter having a pore sizeof 0.45 μm to obtain a polymerizable composition 5.

Example 14

1.0 g of the compound 4 obtained in Example 4, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 6.

Example 15

1.0 g of the compound 5 obtained in Example 5, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.9 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 7.

Example 16

0.5 g of the compound 5 obtained in Example 5, 0.5 g of the compound A,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 2.2 g of cyclopentanoneand 1.7 g of chloroform. The solution was filtered through a disposablefilter having a pore size of 0.45 μm to obtain a polymerizablecomposition 8.

Example 17

1.0 g of the compound 6 obtained in Example 6, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 5.3 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 9.

Example 18

0.2 g of the compound 6 obtained in Example 6, 0.8 g of the compound A,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 3.7 g of chloroform. Thesolution was filtered through a disposable filter having a pore size of0.45 μm to obtain a polymerizable composition 10.

Example 19

0.5 g of the compound 7 obtained in Example 7, 0.5 g of the compound A,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 2.2 g of cyclopentanone.The solution was filtered through a disposable filter having a pore sizeof 0.45 μm to obtain a polymerizable composition 11.

Example 20

0.2 g of the compound 7 obtained in Example 7, 0.8 g of the compound A,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 2.2 g of cyclopentanone.The solution was filtered through a disposable filter having a pore sizeof 0.45 μm to obtain a polymerizable composition 12.

Example 21

0.5 g of the compound 8 obtained in Example 8, 0.5 g of the compound A,30 mg of the photoinitiator A, and 100 mg of a 1% cyclopentanonesolution of the surfactant A were dissolved in 8.0 g of chloroform. Thesolution was filtered through a disposable filter having a pore size of0.45 μm to obtain a polymerizable composition 13.

The polymerizable compositions 1 to 13, 1r, and 2r were polymerized bythe following method to obtain polymers. The retardation was measured,and the wavelength dispersion was evaluated using the resultingpolymers.

Retardation Measurement and Wavelength Dispersion Evaluation I (i)Formation 1 of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 1 to 8, 10 to 12, 1r, and 2r wasapplied to a transparent glass substrate provided with a polyimidealignment film subjected to a rubbing treatment (manufactured by E.H.C.Co. Ltd. (hereinafter the same)) using a #4 wire bar. The resulting filmwas dried for 1 minute at the temperature shown in Table 2, andsubjected to an alignment treatment for 1 minute at the temperatureshown in Table 2 to form a liquid crystal layer. UV rays were applied tothe liquid crystal layer at a dose of 2000 mJ/cm² at the temperatureshown in Table 2 to effect polymerization to prepare a wavelengthdispersion measurement sample.

(ii) Formation 2 of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 9 and 13 was applied to atransparent glass substrate provided with a polyimide alignment filmsubjected to a rubbing treatment using a #6 wire bar. The resulting filmwas dried for 1 minute at the temperature shown in Table 2, andsubjected to an alignment treatment for 1 minute at the temperatureshown in Table 2 to form a liquid crystal layer. UV rays were applied tothe liquid crystal layer at a dose of 2000 mJ/cm² at the temperatureshown in Table 2 to effect polymerization to prepare a wavelengthdispersion measurement sample.

(iii) Measurement of Retardation

The retardation between 400 nm and 800 nm was measured using the sampleutilizing an ellipsometer (“M2000U” manufactured by J. A. Woollam).

(iv) Evaluation of Wavelength Dispersion

The wavelength dispersion was evaluated from the values α and βcalculated by the following expressions using the measured retardation.

α=(retardation at 449.9 nm)/(retardation at 548.5 nm)

β=(retardation at 650.2 nm)/(retardation at 548.5 nm)

The value α is smaller than 1, and the value β is larger than 1 whenideal wideband wavelength dispersion (reverse wavelength dispersion) isachieved. The values α and β are almost identical when flat wavelengthdispersion is achieved. The value α is larger than 1, and the value β issmaller than 1 when normal dispersion is achieved.

Flat wavelength dispersion that ensures that the values α and β arealmost identical is preferable, and reverse wavelength dispersion thatensures that the value α is smaller than 1, and the value β is largerthan 1, is particularly preferable.

Table 2 shows the thickness (μm) of the liquid crystal polymer filmsobtained by polymerizing the polymerizable compositions, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

TABLE 2 Polymer- Polymerizable Polymerizable Alignment izable compoundcompound Drying treatment Exposure Thick- Re composi- Ratio Ratiotemperature temperature temperature ness (548.5 tion Type (%) Type (%)(° C.) (° C.) (° C.) (μm) nm) α β Example 9 1 Compound 1 100 — — 195 2323 1.570 93.58 0.798 1.047 Example 10 2 Compound 2 100 — — 150 100 1001.121 78.11 0.908 1.013 Example 11 3 Compound 3 100 — — 150 100 1001.182 63.49 0.618 1.104 Example 12 4 Compound 3 50 Compound A 50 120 2323 1.543 123.32 0.755 1.024 Example 13 5 Compound 3 50 Compound 2r 50120 23 23 1.321 145.55 0.940 1.004 Example 14 6 Compound 4 100 — — 12023 23 1.604 118.23 0.833 1.034 Example 15 7 Compound 5 100 — — 120 23 231.778 107.68 0.492 1.099 Example 16 8 Compound 5 50 Compound A 50 120 2323 1.024 59.15 0.515 1.094 Example 17 9 Compound 6 100 — — 235 23 232.092 103.85 0.917 1.013 Example 18 10  Compound 6 20 Compound A 80 12023 23 1.720 91.47 0.856 1.036 Example 19 11  Compound 7 50 Compound A 50120 23 23 1.548 98.73 0.863 1.046 Example 20 12  Compound 7 20 CompoundA 80 120 23 23 1.423 103.66 0.853 1.003 Example 21 13  Compound 8 50Compound A 50 180 23 23 1.674 108.05 0.950 1.025 Comparative  1r Compound 1r 100 — — 90 23 23 1.509 355.97 1.193 0.918 Example 1Comparative  2r  Compound 2r 100 — — 80 23 23 1.479 222.90 1.086 0.970Example 2

As is clear from the results shown in Table 2, it was confirmed that thepolymers obtained in Examples 9 to 11 using the compounds 1 to 8according to the invention were an optically anisotropic article. Theoptically anisotropic articles showed ideal wideband wavelengthdispersion in which the value α was smaller than 1, and the value β waslarger than 1.

Example 22 Synthesis of Compound 9

Step 1: Synthesis of Intermediate T

A three-necked reactor equipped with a thermometer was charged with 3.00g (17.69 mmol) of 2-chlorobenzothiazole, 3.26 g (70.74 mmol) ofmethylhydrazine, and 10 ml of methanol under a nitrogen stream toprepare a solution. The solution was refluxed for 1 hour. Aftercompletion of the reaction, the reaction mixture was cooled to 25° C.,and added to 300 ml of distilled water to precipitate crystals. Thecrystals were filtered off, washed with distilled water, and dried undervacuum to obtain 3.01 g of an intermediate T as a white solid (yield:95%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.66 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.36 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.20 (dt, 1H, J=1.0 Hz, 7.5 Hz), 6.99(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.40 (s, 2H), 3.31 (s, 3H)

Step 2: Synthesis of Compound 9

A three-necked reactor equipped with a thermometer was charged with 0.70g (0.75 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 15 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.15 ml (0.15 mmol)of 1 N hydrochloric acid and 0.27 g (1.49 mmol) of the intermediate Tsynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 10 hours. The reaction mixture was concentrated using arotary evaporator, and the concentrate was purified by silica gel columnchromatography (chloroform:THF=98:2) to obtain 0.70 g of a compound 9 asa light yellow solid (yield: 85%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (t, 1H, J=1.5 Hz), 7.66-7.71(m, 2H), 7.64 (s, 1H), 7.35 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.18 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.11 (d, 2H, J=1.5 Hz), 6.99 (d, 2H, J=9.0 Hz), 6.98(d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5Hz), 4.17 (t, 4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 3.73 (s, 3H),2.55-2.76 (m, 4H), 2.25-2.39 (m, 8H), 1.65-1.84 (m, 16H), 1.41-1.55 (m,8H)

Example 23 Synthesis of Compound 10

Step 1: Synthesis of Intermediate U

A three-necked reactor equipped with a thermometer was charged with 3.00g (18.16 mmol) of 2-hydrazinobenzothiazole and 70 ml of DMF under anitrogen stream to prepare a solution. After the addition of 11.83 g(36.32 mmol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 3.12 g (19.97 mmol) of iodoethanedropwise to the mixture over 10 hours, the mixture was stirred at 0° C.for 2 hours, and stirred at 25° C. for 5 hours. After completion of thereaction, 600 ml of distilled water was added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (THF:toluene=1:9) to obtain 1.48 g of an intermediate Uas a white solid (yield: 42%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.65 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.35 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.20 (dt, 1H, J=1.0 Hz, 7.5 Hz), 6.98(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.34 (s, 2H), 3.73 (q, 2H, J=7.0 Hz), 1.20(t, 3H, J=7.0 Hz)

Step 2: Synthesis of Compound 10

A three-necked reactor equipped with a thermometer was charged with 0.70g (0.75 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 15 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.15 ml (0.15 mmol)of 1 N hydrochloric acid and 0.29 g (1.49 mmol) of the intermediate Usynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 10 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=98:2)to obtain 0.67 g of a compound 10 as a light yellow solid (yield: 81%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (dd, 1H, J=1.5 Hz, 2.0 Hz),7.66-7.71 (m, 3H), 7.35 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.17 (dt, 1H, J=1.0Hz, 7.5 Hz), 7.10-7.12 (m, 2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H,J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz),4.38 (q, 2H, J=7.0 Hz), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz),2.55-2.76 (m, 4H), 2.26-2.40 (m, 8H), 1.65-1.84 (m, 16H), 1.41-1.55 (m,8H), 1.34 (t, 3H, J=7.0 Hz)

Example 24 Synthesis of Compound 11

Step 1: Synthesis of Intermediate V

A three-necked reactor equipped with a thermometer was charged with 3.00g (18.16 mmol) of 2-hydrazinobenzothiazole and 70 ml of DMF under anitrogen stream to prepare a solution, After the addition of 11.83 g(36.32 mmol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 3.33 g (27.23 mmol) of 2-bromopropane,the mixture was stirred at 0° C. for 1 hour, and stirred at 25° C. for20 hours. 600 ml of distilled water was added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (THF:toluene=1:9) to obtain 1.11 g of an intermediate Vas a white solid (yield: 29%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.65 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.35 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.20 (dt, 1H, J=1.0 Hz, 7.5 Hz), 6.98(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.10 (s, 2H), 4.61-4.72 (m, 1H), 1.17 (d,6H, J=6.5 Hz)

Step 2: Synthesis of Compound 11

A three-necked reactor equipped with a thermometer was charged with 1.4g (1.49 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.30 ml (0.30 mmol)of 1 N hydrochloric acid and 0.62 g (2.98 mmol) of the intermediate Vsynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 10 hours. The reaction mixture was concentrated using arotary evaporator, and the concentrate was purified by silica gel columnchromatography (chloroform:THF=98:2) to obtain 1.40 g of a compound 11as a light yellow solid (yield: 83%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.08 (s, 1H), 7.74 (d, 1H, J=2.5Hz), 7.69 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.65 (d, 1H, J=8.0 Hz), 7.33 (dt,1H, J=1.0 Hz, 7.5 Hz), 7.16 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.08-7.13 (m,2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.29-5.39 (m, 1H), 4.17 (t, 4H,J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 2.54-2.74 (m, 4H), 2.25-2.39 (m, 8H),1.65-1.84 (m, 16H), 1.62 (d, 6H, J=7.0 Hz), 1.41-1.55 (m, 8H)

Example 25 Synthesis of Compound 12

Step 1: Synthesis of Intermediate W

A three-necked reactor equipped with a thermometer was charged with 3.00g (17.69 mmol) of 2-chlorobenzothiazole, 5.38 g (70.74 mmol) of2-hydrazinoethanol, and 10 ml of methanol under a nitrogen stream toprepare a solution. The solution was refluxed for 2 hours. The reactionmixture was cooled to 25° C., and added to 300 ml of distilled water toprecipitate crystals. The crystals were filtered off, washed withdistilled water, and dried under vacuum to obtain 3.27 g of anintermediate W as a white solid (yield: 88%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.66 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.35 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.20 (dt, 1H, J=1.0 Hz, 7.5 Hz), 6.98(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.37 (s, 2H), 4.86 (t, 1H, J=5.0 Hz),3.69-3.81 (m, 4H)

Step 2: Synthesis of Compound 12

A three-necked reactor equipped with a thermometer was charged with 1.40g (1.50 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.30 ml (0.30 mmol)of 1 N hydrochloric acid and 0.62 g (2.98 mmol) of the intermediate Wsynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 8 hours. The reaction mixture was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (chloroform:THF=98:2) to obtain 1.32 g of a compound 12as a light yellow solid (yield: 78%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.95 (s, 1H), 7.73-7.75 (m, 1H),7.69 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.65 (d, 1H, J=8.0 Hz), 7.35 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.18 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.10-7.13 (m, 2H),6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz),6.88 (d, 2H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.45 (t, 2H,J=5.0 Hz), 4.17 (t, 4H, J=6.5 Hz), 4.04 (q, 2H, J=5.0 Hz), 3.95 (t, 2H,J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.85 (t, 1H, J=5.0 Hz), 2.54-2.74 (m,4H), 2.25-2.39 (m, 8H), 1.65-1.84 (m, 16H), 1.41-1.55 (m, 8H)

Example 26 Synthesis of Compound 13

Step 1: Synthesis of Intermediate X

A three-necked reactor equipped with a thermometer was charged with 3.00g (17.69 mmol) of 2-chlorobenzothiazole, 7.65 g (70.74 mmol) ofphenylhydrazine, and 30 ml of ethylene glycol under a nitrogen stream toprepare a solution. The solution was heated to 140° C., and stirred for5 hours. After completion of the reaction, 300 ml of distilled water wasadded to the reaction mixture, followed by extraction twice with 100 mlof ethyl acetate. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and 15 ml of THF was addedto the concentrate to dissolve the concentrate. The solution was addedto 300 ml of distilled water to precipitate a solid, which was filteredoff. The solid was washed with distilled water, and dried under vacuumto obtain a yellow solid. A flask was charged with the yellow solid.After the addition of 50 ml of toluene, the mixture was stirred for 30minutes, and filtered to remove a toluene-insoluble solid component. Thefiltrate was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (THF:toluene=2:50) toobtain 0.94 g of an intermediate X as a yellow oil (yield: 22%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.01 (dd, 2H, J=1.0 Hz, 9.0 Hz),7.78 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.51 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.43(dd, 2H, J=7.5 Hz, 8.5 Hz), 7.28 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.08-7.16(m, 2H), 6.26 (s, 2H)

Step 2: Synthesis of Compound 13

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.22 ml (0.22 mmol)of 1 N hydrochloric acid and 0.38 g (1.60 mmol) of the intermediate Xsynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 2 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.14 g of a compound 13 as a light yellow solid (yield: 95%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.82 (d, 1H, J=2.5 Hz), 7.73 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.64-7.70 (m, 2H), 7.60 (d, 2H, J=7.5 Hz),7.35-7.42 (m, 3H), 7.30 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.18 (dt, 1H, J=1.0Hz, 7.5 Hz), 7.03-7.12 (m, 2H), 7.00 (d, 2H, J=9.0 Hz), 6.99 (d, 2H,J=9.0 Hz), 6.90 (d, 2H, J=9.0 Hz), 6.89 (d, 2H, J=9.0 Hz), 6.41 (dd, 1H,J=1.5 Hz, 17.5 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H,J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5 Hz), 3.92-3.98 (m, 4H), 2.56-2.71 (m, 2H),2.41-2.50 (m, 1H), 2.27-2.40 (m, 5H), 2.12-2.22 (m, 2H), 1.64-1.91 (m,14H), 1.41-1.56 (m, 10H), 1.19-1.31 (m, 2H)

Example 27 Synthesis of Compound 14

Step 1: Synthesis of Intermediate Y

A three-necked reactor equipped with a thermometer was charged with 2.50g (14.74 mmol) of 2-chlorobenzothiazole, 7.01 g (44.21 mmol) ofp-tolylhydrazine hydrochloride, 7.62 g (58.95 mmol) ofN,N-diisopropylethylamine, and 40 ml of ethylene glycol under a nitrogenstream to prepare a solution. The solution was stirred at 140° C. for 5hours. 400 ml of distilled water was added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator. After the addition of 50 ml of toluene to the concentrate,the mixture was stirred for 30 minutes. A toluene-insoluble solidcomponent was removed by filtration, and the filtrate was concentratedusing a rotary evaporator. The concentrate was purified by silica gelcolumn chromatography (THF:toluene=5:95) to obtain 0.64 g of anintermediate Y as a light yellow solid (yield: 17%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.86 (d, 2H, J=8.5 Hz), 7.76 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.47 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.23 (d, 2H, J=8.5 Hz), 7.09 (dt, 1H, J=1.0 Hz, 7.5Hz), 6.19 (s, 2H), 2.31 (s, 3H)

Step 2: Synthesis of Compound 14

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.22 ml (0.22 mmol)of 1 N hydrochloric acid and 0.32 g (1.28 mmol) of the intermediate Ysynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 1 hour. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.16 g of a compound 14 as a light yellow solid (yield: 93%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.82 (d, 1H, J=2.5 Hz), 7.72 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.61 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.46 (d, 2H,J=8.0 Hz), 7.40 (s, 1H), 7.25-7.32 (m, 3H), 7.17 (dt, 1H, J=1.0 Hz, 7.5Hz), 7.04-7.12 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.92 (m, 4H), 6.41 (dd,1H, J=1.5 Hz, 17.5 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H,J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5Hz), 4.18 (t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5Hz), 2.55-2.72 (m, 2H), 2.50 (s, 3H), 2.41-2.50 (m, 1H), 2.27-2.41 (m,5H), 2.14-2.22 (m, 2H), 1.65-1.95 (m, 14H), 1.41-1.60 (m, 10H),1.22-1.34 (m, 2H)

Example 28 Synthesis of compound 15

Step 1: Synthesis of Intermediate Z

A three-necked reactor equipped with a thermometer was charged with 2.50g (14.74 mmol) of 2-chlorobenzothiazole, 7.72 g (44.21 mmol) of4-methoxyphenylhydrazine hydrochloride, 7.62 g (58.95 mmol) ofN,N-diisopropylethylamine, and 40 ml of ethylene glycol under a nitrogenstream to prepare a solution. The solution was stirred at 140° C. for 5hours. 400 ml of distilled water was added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator. After the addition of 50 ml of toluene to the concentrate,the mixture was stirred for 30 minutes. A toluene-insoluble solidcomponent was removed by filtration. The filtrate was concentrated usinga rotary evaporator, and the concentrate was purified by silica gelcolumn chromatography (THF:toluene=5:95) to obtain 0.84 g of anintermediate Z as a white solid (yield: 21%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.82 (d, 2H, J=9.0 Hz), 7.75 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.43 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.25 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.07 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.01 (d, 2H, J=9.0Hz), 6.15 (s, 2H), 3.78 (s, 3H)

Step 2: Synthesis of Compound 15

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.22 ml (0.22 mmol)of 1 N hydrochloric acid and 0.34 g (1.28 mmol) of the intermediate Zsynthesized in the step 1 to the solution, the mixture was stirred at40° C. for 1 hour. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.18 g of a compound 15 as a light yellow solid (yield: 93%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.82 (d, 1H, J=2.5 Hz), 7.72 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.62 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.39 (s, 1H),7.26-7.33 (m, 3H), 7.13-7.19 (m, 3H), 7.04-7.12 (m, 2H), 6.96-7.02 (m,4H), 6.86-6.92 (m, 4H), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.41 (dd, 1H,J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5 Hz), 4.18 (t, 2H, J=6.5 Hz), 3.95(t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz), 3.88 (s, 3H), 2.55-2.72 (m,2H), 2.25-2.51 (m, 6H), 2.13-2.22 (m, 2H), 1.65-1.96 (m, 14H), 1.41-1.59(m, 10H), 1.19-1.31 (m, 2H)

Example 29 Synthesis of compound 16

Step 1: Synthesis of Intermediate A1

A three-necked reactor equipped with a thermometer was charged with 3.30g (20.0 mmol) of 2-hydrazinobenzothiazole and 75 ml of ethanol under anitrogen stream to prepare a solution. The solution was cooled to 0° C.After the addition of 2.70 g (20.0 mmol) of phenyl isothiocyanate over30 minutes, the mixture was stirred at 0° C. for 3 hours, and stirred at25° C. for 15 hours. After completion of the reaction, a solid thatprecipitated in the reactor was filtered off. The solid was washed withethanol, and dried under vacuum to obtain 4.14 g of an intermediate A1as a white solid (yield: 69%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.22 (s, 1H), 10.09 (s, 2H),7.80 (d, 1H, J=7.5 Hz), 7.46-7.55 (m, 3H), 7.26-7.36 (m, 3H), 7.09-7.19(m, 2H)

Step 2: Synthesis of Compound 16

A three-necked reactor equipped with a thermometer was charged with 2.50g (2.66 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 150 ml of THF under a nitrogenstream to prepare a solution. After the addition of 2.65 ml (2.65 mmol)of 1 N hydrochloric acid and 4.0 g (13.3 mmol) of the intermediate A1synthesized in the step 1 to the solution, the mixture was stirred at60° C. for 30 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=95:5)to obtain 1.40 g of a compound 16 as a light yellow solid (yield: 43%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 11.86 (s, 1H), 8.06 (s, 1H),7.62-7.85 (m, 2H), 7.28-7.59 (m, 4H), 7.06-7.25 (m, 4H), 6.80-7.05 (m,10H), 6.40 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.40 (dd, 1H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz),4.18 (t, 2H, J=6.5 Hz), 4.17 (t, 2H, J=6.5 Hz), 3.89-3.98 (m, 4H),2.50-2.76 (m, 2H), 2.21-2.48 (m, 6H), 1.99-2.16 (m, 2H), 1.35-1.85 (m,26H)

Example 30 Synthesis of Compound 17

Step 1: Synthesis of Intermediate B1

A three-necked reactor equipped with a thermometer was charged with 2.30g (2.45 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 25 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.49 ml (0.49 mmol)of 1 N hydrochloric acid to the solution, a solution prepared bydissolving 0.40 g (2.45 mol) of 2-hydrazinobenzothiazole in 5 ml of THFwas added dropwise to the mixture over 15 minutes. After the dropwiseaddition, the mixture was stirred at 25° C. for 1 hour. After completionof the reaction, the reaction mixture was added to 400 ml of methanol toprecipitate a solid, which was filtered off. The solid was dried using avacuum dryer to obtain 2.4 g of an intermediate B1 as a light yellowsolid (yield: 90%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.63 (s, 1H), 8.10 (s, 1H), 7.80(d, 1H, J=5.0 Hz), 7.60 (d, 1H, J=3.0 Hz), 7.48 (s, 1H), 7.21-7.35 (m,3H), 7.14 (t, 11, J=7.5 Hz), 6.98-7.05 (m, 4H), 6.91-6.97 (m, 4H), 6.32(dd, 2H, J=1.5 Hz, 17.5 Hz), 6.18 (dd, 2H, J=10.0 Hz, 17.5 Hz), 5.93(dd, 2H, J=1.5 Hz, 10.0 Hz), 4.12 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5Hz), 2.56-2.83 (m, 4H), 2.11-2.30 (m, 8H), 1.52-1.80 (m, 16H), 1.33-1.49(m, 8H)

Step 2: Synthesis of Compound 17

A three-necked reactor equipped with a thermometer was charged with 2.00g (1.84 mmol) of the intermediate B1 synthesized in the step 1, 0.02 g(0.18 mmol) of 4-(dimethylamino)pyridine, and 100 ml of THF under anitrogen stream to prepare a solution. After the addition of 0.33 g(2.03 mmol) of n-octanoyl chloride to the solution, the reactor wasimmersed in an ice bath to adjust the temperature of the reactionmixture to 10° C. After the addition of 0.22 g (2.21 mmol) oftriethylamine dropwise to the reaction mixture over 10 minutes, themixture was stirred at 25° C. for 2 hours. After completion of thereaction, 600 ml of distilled water and 10 ml of a saturated sodiumchloride solution were added to the reaction mixture, followed byextraction twice with 200 ml of chloroform. The organic layer was driedover anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The reaction mixture was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (chloroform:THF=40:2) to obtain 1.72 g of a compound 17as a light yellow solid (yield: 77%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.89 (s, 1H), 7.89-7.98 (m, 2H),7.78 (d, 1H, J=2.5 Hz), 7.53 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.42 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.20 (dd, 1H, J=2.5 Hz, 9.0 Hz), 7.14 (d, 1H, J=9.0Hz), 6.98 (d, 2H, J=9.0 Hz), 6.96 (d, 2H, J=9.0 Hz), 6.89 (d, 2H, J=9.0Hz), 6.88 (d, 2H, J=9.0 Hz), 6.40 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.40 (dd,1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.13 (dd, 1H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.82 (dd, 1H,J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5 Hz), 4.17 (t, 2H, J=6.5 Hz),3.92-3.98 (m, 4H), 3.01 (t, 2H, J=7.5 Hz), 2.54-2.70 (m, 2H), 2.39-2.48(m, 1H), 2.23-2.37 (m, 5H), 1.91-2.06 (m, 4H), 1.62-1.86 (m, 14H),1.26-1.56 (m, 20H), 0.90 (t, 3H, J=7.0 Hz)

Example 31 Synthesis of Compound 18

Step 1: Synthesis of Intermediate C1

A four-necked reactor equipped with a thermometer was charged with 2.50g (16.6 mmol) of cyclohexylhydrazine hydrochloride and 8 ml oftriethylamine under a nitrogen stream to prepare a solution. After theaddition of 5.63 g (33.2 mmol) of 2-chlorobenzothiazole to the solution,the mixture was stirred at 80° C. for 5 hours. After completion of thereaction, the reaction mixture was cooled to 20° C., added to 150 ml ofa saturated sodium hydrogen carbonate aqueous solution, and extractedwith 300 ml of ethyl acetate. After drying the ethyl acetate layer overanhydrous sodium sulfate, sodium sulfate was separated by filtration.Ethyl acetate was evaporated from the filtrate under reduced pressureusing a rotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (hexane:ethylacetate=75:25) to obtain 1.02 g of an intermediate C1 as a white solid(yield: 22.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 7.58 (d, 1H, J=7.8 Hz), 7.52 (d,1H, J=8.2 Hz), 7.26 (dd, 1H, J=7.4 Hz, 8.2 Hz), 7.05 (dd, 1H, J=7.4 Hz,7.8 Hz), 4.25-4.32 (m, 1H), 4.04 (s, 2H), 1.84-1.88 (m, 4H), 1.68-1.73(m, 1H), 1.43-1.59 (m, 4H), 1.08-1.19 (m, 1H)

Step 2: Synthesis of Compound 18

A three-necked reactor equipped with a thermometer was charged with 1.04g (1.49 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 456 mg (1.84 mmol) of theintermediate C1 synthesized in the step 1, 38.6 mg (0,166 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (chloroform:THF=97:3) toobtain 1.24 g of a compound 18 as a light yellow solid (yield: 71.4%).

The structure of the target product was identified by ¹H-NMR,

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.15 (s, 1H), 7.72 (d, 1H, J=1.5Hz), 7.68 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.66 (dd, 1H, J=1.5 Hz, 8.0 Hz),7.31-7.35 (m, 1H), 7.14-7.18 (m, 1H), 7.13 (d, 1H, J=9.0 Hz), 7.10 (dd,1H, J=1.5 Hz, 9.0 Hz), 6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.40 (dd,2H, J=1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J=10.0 Hz, 17.0 Hz), 5.82 (dd, 2H,J=1.5 Hz, 10.0 Hz), 4.62-4.70 (m, 1H), 4.17 (t, 4H, J=6.5 Hz), 3.94 (t,4H, J=6.5 Hz), 2.55-2.74 (m, 4H), 2.27-2.47 (m, 10H), 1.90-2.00 (m, 4H),1.65-1.85 (m, 16H), 1.42-1.55 (m, 10H), 1.24-1.33 (m, 2H)

Example 32 Synthesis of Compound 19

Step 1: Synthesis of Intermediate D1

A four-necked reactor equipped with a thermometer was charged with 5.00g (30.3 mmol) of 2-hydrazinobenzothiazole and 100 ml of DMF under anitrogen stream to prepare a solution. After the addition of 20.9 g (152mmol) of potassium carbonate and 5.17 g (30.3 mmol) of5-bromovaleronitrile to the solution, the mixture was stirred at 60° C.for 8 hours. After completion of the reaction, the reaction mixture wascooled to 20° C., added to 500 ml of water, and extracted with 500 ml ofethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (n-hexane:ethylacetate=60:40) to obtain 3.41 g of an intermediate D1 as a white solid(yield: 45.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 7.60 (d, 1H, J=7.8 Hz), 7.51 (d,1H, J=8.1 Hz), 7.28 (dd, 1H, J=7.3, 8.1 Hz), 7.07 (dd, 1H, J=7.3 Hz, 7.8Hz), 4.23 (s, 2H), 3.81 (t, 2H, J=6.9 Hz), 2.46 (t, 2H, J=7.1 Hz),1.88-1.95 (m, 2H), 1.71-1.79 (m, 2H)

Step 2: Synthesis of Compound 19

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 438 mg (1.78 mmol) of theintermediate D1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=85:15) to obtain 1.31 g of a compound 19 as a light yellow solid(yield: 70.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=1.5 Hz), 7.64-7.72(m, 3H), 7.35 (ddd, 1H, J=1.5 Hz, 8.0 Hz, 8.0 Hz), 7.19 (ddd, 1H, J=1.5Hz, 8.0 Hz, 8.0 Hz), 7.10-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.0 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.22 (t, 2H, J=6.5 Hz), 4.18 (t,4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.58-2.75 (m, 4H), 2.55 (t, 2H,J=6.5 Hz), 2.26-2.40 (m, 8H), 1.96 (tt, 2H, J=6.5 Hz, 6.5 Hz), 1.66-1.83(m, 18H), 1.42-1.55 (m, 8H)

Example 33 Synthesis of Compound 20

Step 1: Synthesis of Intermediate E1

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 3.28 g (14.5 mmol) of iodineheptane tothe mixture over 5 minutes, the mixture was stirred at 25° C. for 3hours. After completion of the reaction, 200 ml of water was added tothe reaction mixture, followed by extraction twice with 100 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (n-hexane:ethyl acetate=85:15) toobtain 1.81 g of an intermediate E1 as a white solid (yield: 56.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.59 (dd, 1H, J=1.5 Hz, 8.0 Hz),7.53 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.06-7.28 (m, 2H), 4.22 (s, 2H), 3.75(t, 2H, J=7.0 Hz), 1.29-1.38 (m, 10H), 0.88 (t, 3H, J=7.0 Hz)

Step 2: Synthesis of Compound 20

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 468 mg (1.78 mmol) of theintermediate E1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.46 g of a compound 20 as a light yellow solid (yield:77.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=1.5 Hz), 7.66-7.70(m, 3H), 7.34 (ddd, 1H, J=1.5 Hz, 8.0 Hz, 8.0 Hz), 7.17 (ddd, 1H, J=1.5Hz, 8.0 Hz, 8.0 Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.87-6.90 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J=7.0 Hz), 4.18 (t,4H, J=7.0 Hz), 3.95 (t, 4H, J=7.0 Hz), 2.55-2.73 (m, 4H), 2.26-2.40 (m,8H), 1.65-1.84 (m, 16H), 1.36-1.55 (m, 14H), 1.25-1.35 (m, 4H), 0.87 (t,3H, J=7.0 Hz)

Example 34 Synthesis of Compound 21

Step 1: Synthesis of Intermediate F1

A four-necked reactor equipped with a thermometer was charged with 3.00g (18.2 mmol) of 2-hydrazinobenzothiazole and 45 ml of DMF under anitrogen stream to prepare a solution. After the addition of 11.9 g(36.4 mmol) of cesium carbonate and 6.45 g (21.8 mmol) of 1-iododecaneto the solution, the mixture was stirred at 25° C. for 20 hours. Aftercompletion of the reaction, the reaction mixture was added to 200 ml ofwater, and extracted with 300 ml of ethyl acetate. After drying theethyl acetate layer over anhydrous sodium sulfate, sodium sulfate wasseparated by filtration. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a yellowsolid. The yellow solid was purified by silica gel column chromatography(toluene:ethyl acetate=95:5) to obtain 2.93 g of an intermediate F1 as awhite solid (yield: 48.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.53 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz), 4.22 (s, 2H), 3.74 (t,2H, J=7.5 Hz), 1.73 (tt, 2H, J=7.5 Hz, 7.5 Hz), 1.41-1.25 (m, 18H), 0.88(t, 3H, J=7.0 Hz)

Step 2: Synthesis of Compound 21

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 592 mg (1.78 mmol) of theintermediate F1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.44 g of a compound 21 as a light yellow solid (yield:71.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=1.5 Hz), 7.66-7.70(m, 3H), 7.34 (ddd, 1H, J=1:5 Hz, 7.5 Hz, 7.5 Hz), 7.17 (ddd, 1H, J=1.5Hz, 7.5 Hz, 7.5 Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.86-6.91 (m,4H), 6.41 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J=7.0 Hz), 4.18 (t,4H, J=7.0 Hz), 3.94 (t, 4H, J=7.0 Hz), 2.56-2.73 (m, 4H), 2.28-2.39 (m,8H), 1.66-1.84 (m, 18H), 1.35-1.55 (m, 10H), 1.19-1.33 (m, 16H), 0.86(t, 3H, J=7.0 Hz)

Example 35 Synthesis of Compound 22

Step 1: Synthesis of Intermediate G1

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 1.98 g (14.5 mmol) of butyl 2-chloroethylether to the mixture over 5 minutes, the mixture was stirred at 25° C.for 3 hours. After completion of the reaction, 200 ml of water was addedto the reaction mixture, followed by extraction twice with 100 ml ofethyl acetate. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (n-hexane:ethylacetate=75:25) to obtain 1.70 g of an intermediate G1 as a white solid(yield: 53.0%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.61 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.50 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.27-7.29 (m, 1H), 7.04-7.08 (m, 1H),4.70 (s, 2H), 4.01 (t, 2H, J=5.0 Hz), 3.82 (t, 2H, J=5.0 Hz), 3.44 (t,2H, J=7.0 Hz), 1.52-1.57 (m, 2H), 1.31-1.39 (m, 2H), 0.90 (t, 3H, J=7.0Hz)

Step 2: Synthesis of Compound 22

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 396 mg (1.78 mmol) of theintermediate G1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.31 g of a compound 22 as a light yellow solid (yield:69.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.03 (s, 1H), 7.76 (d, 1H, J=1.5Hz), 7.65-7.71 (m, 2H), 7.34 (ddd, 1H, J=1.5 Hz, 8.0 Hz, 8.0 Hz), 7.17(ddd, 1H, J=1.5 Hz, 8.0 Hz, 8.0 Hz), 7.09-7.12 (m, 2H), 6.96-7.00 (m,4H), 6.87-6.90 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.45 (t, 2H,J=5.5 Hz), 4.18 (t, 4H, J=7.0 Hz), 3.95 (t, 4H, J=7.0 Hz), 3.79 (t, 2H,J=5.5 Hz), 3.44 (t, 2H, J=7.0 Hz), 2.55-2.74 (m, 4H), 2.28-2.40 (m, 8H),1.65-1.83 (m, 16H), 1.42-1.55 (m, 10H), 1.25-1.34 (m, 2H), 0.85 (t, 3H,J=7.0 Hz)

Example 36 Synthesis of Compound 23

A three-necked reactor equipped with a thermometer was charged with 2.00g (1.84 mmol) of the intermediate B1 synthesized in the step 1 ofExample 30 (see “Synthesis of compound 17”) and 20 ml of THF under anitrogen stream to prepare a solution. The solution was cooled to 0° C.After the addition of 344 mg (2.76 mmol) of 2-methoxyethoxymethylchloride to the solution, a solution prepared by dissolving 476 mg (3.68mol) of N,N-diisopropylethylamine in 5 ml of THF was added dropwise tothe mixture over 5 minutes. After the dropwise addition, the mixture wasstirred at 25° C. for 20 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (chloroform:THF=95:5) toobtain 1.58 g of a compound 23 as a light yellow solid (yield: 73.0%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.31 (s, 1H), 7.62-7.71 (m, 2H),7.32-7.42 (m, 2H), 7.25-7.29 (m, 2H), 7.15-7.19 (m, 1H), 7.00-7.04 (m,4H), 6.92-6.96 (m, 4H), 6.32 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.17 (dd, 2H,J=10.5 Hz, 17.5 Hz), 5.93 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.60 (s, 2H),4.12 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 3.71 (t, 2H, J=6.0 Hz),3.46 (t, 2H, J=6.0 Hz), 3.20 (s, 3H), 2.60-2.85 (m, 4H), 2.11-2.28 (m,8H), 1.55-1.75 (m, 16H), 1.35-1.50 (m, 8H)

Example 37 Synthesis of Compound 24

Step 1: Synthesis of Compound 24

A three-necked reactor equipped with a thermometer was charged with 2.00g (1.84 mmol) of the intermediate B1 synthesized in the step 1 ofExample 30 (see “Synthesis of compound 17”) and 20 ml of THF under anitrogen stream to prepare a solution. The solution was cooled to 0° C.After the addition of 412 mg (2.76 mmol) of chloromethyl cyclohexylether to the solution, a solution prepared by dissolving 476 mg (7.36mol) of N,N-diisopropylethylamine in 5 ml of THF was added dropwise tothe mixture over 5 minutes. After the dropwise addition, the mixture wasstirred at 25° C. for 3 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=95:5) to obtain 1.54 g of a compound 24 as a light yellow solid(yield: 70.0%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.33 (s, 1H), 7.86 (d, 1H, J=2.0Hz), 7.42 (d, 1H, J=7.5 Hz), 7.25-7.29 (m, 2H), 7.08-7.13 (m, 3H),6.96-7.00 (m, 4H), 6.86-6.90 (m, 4H), 6.41 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz),5.62 (s, 2H), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 3.56-3.64(m, 1H), 2.57-2.76 (m, 4H), 2.27-2.40 (m, 8H), 1.89-1.95 (m, 2H),1.64-1.83 (m, 16H), 1.42-1.55 (m, 10H), 1.18-1.39 (m, 6H)

Example 38 Synthesis of Compound 25

Step 1: Synthesis of Intermediate H1

A three-necked reactor equipped with a thermometer was charged with 7.28g (66.1 mmol) of hydroquinone, 2.38 g (59.5 mmol) of sodium hydroxide,and 50 ml of distilled water under a nitrogen stream. 9.90 g (60.1 mol)of 8-chloro-1-n-octanol was added dropwise to the solution over 30minutes. After the dropwise addition, the mixture was refluxed for 5hours. After completion of the reaction, the reaction mixture was cooledto 25° C. to precipitate a white solid, which was filtered off. Thesolid was recrystallized from 120 ml of toluene to obtain 7.93 g of anintermediate H1 as a white solid (yield: 56.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 8.0 Hz), 6.65 (dd, 2H, J=2.5 Hz, 8.0 Hz), 4.33 (t, 1H, J=5.0 Hz),3.82 (t, 2H, J=6.5 Hz), 3.37 (dt, 2H, J=5.0 Hz, 6.5 Hz), 1.65 (tt, 2H,J=6.5 Hz, 6.5 Hz), 1.28-1.42 (m, 10H)

Step 2: Synthesis of Intermediate I1

A three-necked reactor equipped with a thermometer was charged with 7.84g (32.9 mmol) of the intermediate H1 synthesized by the step 1, 2.61 g(36.2 mmol) of acrylic acid, 40.8 mg (0.329 mmol) of 4-methoxyphenol,316 mg (3.29 mmol) of methanesulfonic acid, and 40 ml of toluene under anitrogen stream. The mixture was refluxed for 6 hours. After cooling thereaction mixture to 25° C., the reaction mixture was added to 200 ml ofwater, and extracted with 100 ml of ethyl acetate. After drying theethyl acetate layer over anhydrous sodium sulfate, sodium sulfate wasseparated by filtration. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a brownsolid. The brown solid was purified by silica gel column chromatography(toluene:THF=95:5) to obtain 6.95 g of an intermediate 11 as a whitesolid (yield: 71.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.86 (s, 1H), 6.72 (dd, 2H, J=2.5Hz, 9.0 Hz), 6.65 (dd, 2H, J=2.5 Hz, 8.0 Hz), 6.31 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.17 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz,10.5 Hz), 4.10 (t, 2H, J=6.5 Hz), 3.83 (t, 2H, J=6.5 Hz), 1.58-1.68 (m,4H), 1.30-1.39 (m, 8H)

Step 3: Synthesis of Intermediate J1

A three-necked reactor equipped with a thermometer was charged with 6.86g (39.8 mmol) of trans-1,4-cyclohexanedicarboxylic acid, 70 ml of THF,and 14 ml of DMF under a nitrogen stream. After the addition of 2.28 g(19.9 mmol) of methanesulfonyl chloride to the mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 20° C. 2.20 g (21.7 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes while maintaining the temperatureof the reaction mixture at 20 to 30° C. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After the addition of 221 mg(1.81 mmol) of 4-(dimethylamino)pyridine and 5.30 g (18.1 mmol) of theintermediate I1 synthesized in the step 2 to the reaction mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. 2.20 g (21.7 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 300 ml of distilled water and 100 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (toluene:THF=85:15) to obtain 5.23 g of an intermediateJ2 as a white solid (yield: 64.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.1 (s, 1H), 6.98 (dd, 2H, J=2.5Hz, 9.0 Hz), 6.92 (dd, 2H, J=2.5 Hz, 8.0 Hz), 6.31 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.17 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.92 (dd, 1H, J=1.5 Hz,10.5 Hz), 4.10 (t, 2H, J=6.5 Hz), 3.93 (t, 2H, J=6.5 Hz), 2.19-2.25 (m,1H), 2.04-2.10 (m, 2H), 1.94-1.98 (m, 2H), 1.69 (tt, 2H, J=6.5 Hz, 6.5Hz), 1.57-1.64 (m, 2H), 1.31-1.52 (m, 13H)

Step 4: Synthesis of Intermediate K1

A three-necked reactor equipped with a thermometer was charged with 4.00g (8.96 mmol) of the intermediate J1 synthesized in the step 3 and 60 mlof THF under a nitrogen stream to prepare a solution. After the additionof 1.07 g (9.32 mmol) of methanesulfonyl chloride to the solution, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 20° C. 944 mg (9.32 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. After theaddition of 92.0 mg (0.748 mmol) of 4-(dimethylamino)pyridine and 548 mg(3.97 mmol) of 2,5-dihydroxybenzaldehyde to the reaction mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. 944 mg (9.32 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 350 ml of distilled water and 50 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 150 ml of chloroform. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was dissolved in 15 ml of THF. 200 ml ofmethanol was added to the solution to precipitate crystals, which werefiltered off. The crystals were washed with methanol, and dried undervacuum to obtain 2.85 g of an intermediate K1 as a white solid (yield:72.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.1 (s, 1H), 7.61 (d, 1H, J=2.5Hz), 7.37 (dd, 1H, J=2.5 Hz, 8.5 Hz), 7.20 (d, 1H, J=8.5 Hz), 6.97 (dd,4H, J=2.0 Hz, 9.0 Hz), 6.88 (dd, 4H, J=2.0 Hz, 9.0 Hz), 6.40 (dd, 2H,J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H,J=1.5 Hz, 10.5 Hz), 4.16 (t, 4H, J=6.5 Hz), 3.93 (t, 4H, J=6.5 Hz),2.57-2.74 (m, 4H), 2.26-2.37 (m, 8H), 1.65-1.80 (m, 16H), 1.35-1.48 (m,16H)

Step 5: Synthesis of Compound 25

A three-necked reactor equipped with a thermometer was charged with 1.95g (1.96 mmol) of the intermediate K1 synthesized in the step 4, 441 mg(1.76 mmol) of the intermediate J synthesized in the step 1 of Example 4(see “Synthesis of compound 4”), 45.6 mg (0.196 mmol) of(±)-10-camphorsulfonic acid, 24 ml of THF, and 6 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The chloroform layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. Chloroform wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (toluene:ethyl acetate=95:5) to obtain1.56 g of a compound 25 as a light yellow solid (yield: 64.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=1.5 Hz), 7.66-7.70(m, 3H), 7.34 (dd, 1H, J=1.5 Hz, 7.8 Hz), 7.09-7.18 (m, 3H), 6.96-7.00(m, 4H), 6.86-6.90 (m, 4H), 6.41 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd,2H, J=10.5 Hz, 17.5 Hz), 5.81 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H,J=7.5 Hz), 4.16 (t, 4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 2.56-2.72 (m,4H), 2.27-2.38 (m, 8H), 1.65-1.81 (m, 18H), 1.32-1.49 (m, 22H), 0.90 (t,3H, J=7.5 Hz)

Example 39 Synthesis of Compound 26

Step 1: Synthesis of Intermediate L1

A four-necked reactor equipped with a thermometer was charged with 5.00g (30.3 mmol) of 2-hydrazinobenzothiazole and 50 ml of DMF under anitrogen stream to prepare a solution. After the addition of 14.8 g(45.5 mmol) of cesium carbonate and 3.1 ml (36.3 mmol) of allyl bromideto the solution, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, the reaction mixture was added to 200 ml ofwater, and extracted with 300 ml of ethyl acetate. After drying theethyl acetate layer over anhydrous sodium sulfate, sodium sulfate wasseparated by filtration. Ethyl acetate was evaporated from the filtrateunder reduced pressure using a rotary evaporator to obtain a yellowsolid. The yellow solid was purified by silica gel column chromatography(hexane:ethyl acetate=70:30) to obtain 1.82 g of an intermediate L1 as awhite solid (yield: 29.0%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.62 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.54 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.29 (ddd, 1H, J=1.0 Hz, 7.0 Hz, 8.0Hz), 7.08 (ddd, 1H, J=1.0 Hz, 7.0 Hz, 7.5 Hz), 5.90 (ddt, 1H, J=6.5 Hz,10.5 Hz, 17.0 Hz), 5.38 (ddt, 1H, J=1.0 Hz, 2.5 Hz, 10.5 Hz), 5.34 (ddt,1H, J=1.5 Hz, 2.5 Hz, 17.0 Hz), 4.42 (ddd, 2H, J=1.0 Hz, 1.5 Hz, 6.5Hz), 4.18 (s, 2H)

Step 2: Synthesis of Compound 26

A four-necked reactor equipped with a thermometer was charged with 368mg (1.77 mmol) of the intermediate L1 synthesized in the step 1, 1.50 g(1.60 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 15 ml of THF undera nitrogen stream to prepare a solution. After the addition of 41.2 mg(0.18 mmol) of (±)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.61 g of a compound 26 as a yellow solid(yield: 89.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=2.5 Hz), 7.70 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.64-7.69 (m, 2H), 7.35 (ddd, 1H, J=1.0 Hz, 7.5Hz, 8.0 Hz), 7.18 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 7.09-7.13 (m,2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.88 (ddt, 1H, J=4.5 Hz, 10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz,10.5 Hz), 5.29 (dd, 1H, J=1.0 Hz, 10.5 Hz), 5.19 (dd, 1H, J=1.0 Hz, 17.5Hz), 4.98-4.99 (m, 2H), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz),2.57-2.67 (m, 4H), 2.30-2.35 (m, 8H), 1.76-1.85 (m, 4H), 1.66-1.74 (m,12H), 1.42-1.54 (m, 8H)

Example 40 Synthesis of Compound 27

Step 1: Synthesis of Intermediate M1

A four-necked reactor equipped with a thermometer was charged with 5.04g (30.5 mmol) of 2-hydrazinobenzothiazole and 50 ml of DMF under anitrogen stream to prepare a solution. After the addition of 14.9 g(45.8 mmol) of cesium carbonate and 4.94 g (36.6 mmol) of4-bromo-1-butene to the solution, the mixture was stirred at 25° C. for7 hours. After completion of the reaction, the reaction mixture wasadded to 200 ml of water, and extracted with 300 ml of ethyl acetate.After drying the ethyl acetate layer over anhydrous sodium sulfate,sodium sulfate was separated by filtration. Ethyl acetate was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a yellow solid. The yellow solid was purified by silica gelcolumn chromatography (hexane:ethyl acetate=70:30) to obtain 4.40 g ofan intermediate M1 as a white solid (yield: 49.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.54 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.28 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0Hz), 7.06 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz), 5.89 (ddt, 1H, J=7.0 Hz,10.5 Hz, 17.0 Hz), 5.17 (ddt, 1H, J=1.5 Hz, 3.0 Hz, 17.0 Hz), 5.09 (ddt,1H, J=1.0 Hz, 3.0 Hz, 10.5 Hz), 4.26 (s, 2H), 3.85 (t, 2H, J=7.0 Hz),2.52 (dddt, 2H, J=1.0 Hz, 1.5 Hz, 7.0 Hz, 7.0 Hz)

Step 2: Synthesis of Compound 27

A four-necked reactor equipped with a thermometer was charged with 195mg (1.77 mmol) of the intermediate M1 synthesized in the step 1, 1.50 g(1.60 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 15 ml of THF undera nitrogen stream to prepare a solution. After the addition of 41.2 mg(0.18 mmol) of (1)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 8 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.26 g of a compound 27 as a yellow solid(yield: 69.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.76 (d, 1H, J=2.5 Hz), 7.67-7.70(m, 3H), 7.35 (ddd, 1H, J=1.5 Hz, 7.5 Hz, 8.0 Hz), 7.18 (ddd, 1H, J=1.5Hz, 7.5 Hz, 8.0 Hz), 7.10-7.14 (m, 2H), 6.99 (d, 2H, J=9.5 Hz), 6.98 (d,2H, J=9.5 Hz), 6.88 (d, 4H, J=9.5 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.89 (ddt, 1H, J=6.5 Hz, 10.5 Hz,17.0 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.18 (dd, 1H, J=1.5 Hz, 17.0Hz), 5.15 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.38 (t, 2H, J=7.0 Hz), 4.18 (t,4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.58-2.68 (m, 4H), 2.51 (dt, 2H,J=6.5 Hz, 7.0 Hz), 2.31-2.35 (m, 8H), 1.76-1.85 (m, 4H), 1.65-1.74 (m,12H), 1.41-1.54 (m, 8H)

Example 41 Synthesis of Compound 28

Step 1: Synthesis of Intermediate N1

A four-necked reactor equipped with a thermometer was charged with 1.45g (8.75 mmol) of 2-hydrazinobenzothiazole and 20 ml of DMF under anitrogen stream to prepare a solution. After the addition of 3.63 g(26.3 mmol) of potassium carbonate and 2.50 g (10.5 mmol) of1,1,1-trifluoro-4-iodobutane the solution, the mixture was stirred at80° C. for 8 hours. After completion of the reaction, the reactionmixture was cooled to 20° C., added to 200 ml of water, and extractedwith 300 ml of ethyl acetate. After drying the ethyl acetate layer overanhydrous sodium sulfate, sodium sulfate was separated by filtration.Ethyl acetate was evaporated from the filtrate under reduced pressureusing a rotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (n-hexane:ethylacetate=85:15) to obtain 961 mg of an intermediate N1 as a white solid(yield: 39.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.61 (d, 1H, J=8.0 Hz), 7.54 (d,1H, J=7.8 Hz), 7.30 (dd, 1H, J=7.8 Hz, 7.8 Hz), 7.09 (dd, 1H, J=7.8 Hz,8.0 Hz), 4.24 (s, 2H), 3.81 (t, 2H, J=7.0 Hz), 2.16-2.26 (m, 2H),1.99-2.05 (m, 2H)

Step 2: Synthesis of Compound 28

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 489 mg (1.78 mmol) of theintermediate N1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (chloroform:THF=9:1) toobtain 1.47 g of a compound 28 as a light yellow solid (yield: 77.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (s, 1H), 7.65-7.71 (m, 3H),7.34 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 7.17 (ddd, 1H, J=1.0 Hz, 7.5Hz, 7.5 Hz), 7.08-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H),6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz),5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.42 (t, 2H, J=7.5 Hz), 4.18 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.55-2.73 (m, 4H), 2.25-2.38 (m,10H), 2.04 (tt, 2H, J=7.5 Hz, 7.5 Hz), 1.64-1.84 (m, 16H), 1.42-1.55 (m,8H)

Example 42 Synthesis of Compound 29

Step 1: Synthesis of Intermediate 01

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 2.39 g (14.5 mmol) of 2-bromohexane tothe mixture over 5 minutes, the mixture was stirred at 25° C. for 3hours. After completion of the reaction, 200 ml of water was added tothe reaction mixture, followed by extraction twice with 100 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (n-hexane:ethyl acetate=93:7) toobtain 1.61 g of an intermediate O1 as a white solid (yield: 53.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 7.59 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.52 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.24-7.30 (m, 1H), 7.05 (ddd, 1H, J=1.0Hz, 8.0 Hz, 8.0 Hz), 3.97 (s, 2H), 1.47-1.74 (m, 3H), 1.20-1.41 (m, 7H),0.89 (t, 3H, J=5.5 Hz)

Step 2: Synthesis of Compound 29

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 444 mg (1.78 mmol) of theintermediate 01 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=92:8) to obtain 1.35 g of a compound 29 as a light yellow solid(yield: 72.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.04 (s, 1H), 7.73 (d, 1H, J=1.5Hz), 7.69 (dd, 1H, J=1.5 Hz, 7.8 Hz), 7.65 (dd, 1H, J=1.5 Hz, 7.8 Hz),7.33 (ddd, 1H, J=1.5 Hz, 7.8 Hz, 7.8 Hz), 7.07-7.19 (m, 3H), 6.95-7.01(m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd,2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.54-2.73 (m, 4H), 2.25-2.40 (m, 8H),1.65-1.83 (m, 16H), 1.60-1.62 (m, 2H), 1.57 (d, 3H, J=7.5 Hz), 1.24-1.55(m, 13H), 0.87 (t, 3H, J=7.5 Hz)

Example 43 Synthesis of Compound 30

Step 1: Synthesis of Intermediate P1

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 2.60 g (14.5 mmol) of 3-bromoheptane tothe mixture over 5 minutes, the mixture was stirred at 25° C. for 3hours. After completion of the reaction, 200 ml of water was added tothe reaction mixture, followed by extraction twice with 100 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (n-hexane:ethyl acetate=9:1) toobtain 1.80 g of an intermediate P1 as a white solid (yield: 56.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.58 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.51 (dd, 1H, J=0.0 Hz, 7.5 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5Hz), 7.04 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 3.94 (s, 2H), 1.48-1.72(m, 5H), 1.18-1.41 (m, 4H), 0.91 (t, 3H, J=7.5 Hz), 0.86 (t, 3H, J=7.5Hz)

Step 2: Synthesis of Compound 30

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 468 mg (1.78 mmol) of theintermediate P1 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.44 g of a compound 20 as a light yellow solid (yield:76.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.03 (s, 1H), 7.74 (d, 1H, J=3.0Hz), 7.69 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.64 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.33 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0 Hz), 7.16 (ddd, 1H, J=1.0 Hz, 8.0Hz, 8.0 Hz), 7.07-7.14 (m, 2H), 6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H),6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5 Hz),5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H,J=6.5 Hz), 2.55-2.72 (m, 4H), 2.26-2.40 (m, 8H), 1.65-1.91 (m, 19H),1.23-1.55 (m, 14H), 0.94 (t, 3H, J=7.5 Hz), 0.86 (t, 3H, J=7.5 Hz)

Example 44 Synthesis of Compound 31

Step 1: Synthesis of Intermediate Q1

A three-necked reactor equipped with a thermometer was charged with 14.4g (54.4 mmol) of 12-bromo-1-dodecanol, 12.0 g (59.8 mmol) of4-(benzyloxy)phenol, 9.02 g (65.2 mmol) of potassium carbonate, 1.42 g(5.44 mmol) of 18-crown-6 ether, and 150 ml of acetone. The mixture wasrefluxed for 10 hours. After completion of the reaction, the reactionmixture was cooled to 25° C. 300 ml of distilled water was added to thereaction mixture, followed by extraction twice with 200 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator to obtain 12.2 g of anintermediate Q1 as a white solid (yield: 51.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.36-7.45 (m, 4H), 7.29-7.34 (m,1H), 6.89-6.94 (m, 2H), 6.81-6.86 (m, 2H), 5.02 (s, 2H), 4.32 (t, 1H,J=5.0 Hz), 3.87 (t, 2H, J=7.5 Hz), 3.36 (t, 2H, J=7.5 Hz), 1.66 (tt, 2H,J=7.5 Hz, 7.5 Hz), 1.20-1.43 (m, 18H)

Step 2: Synthesis of Intermediate R1

A three-necked reactor equipped with a thermometer was charged with 12.2g (27.8 mmol) of the intermediate Q1 synthesized in the step 1, 2.22 gof 5% palladium-activated carbon, 50 ml of THF, and 200 ml of methanol.A hydrogen balloon was provided to the reactor, and the mixture wasstirred at 25° C. for 21 hours in a hydrogen atmosphere. Aftercompletion of the reaction, 100 ml of chloroform was added to thereaction mixture, and palladium-activated carbon was separated byfiltration. The organic layer was concentrated using a rotary evaporatorto obtain 8.70 g of a brown powder. The brown powder was dissolved in100 ml of toluene (20 g). After the addition of 2.34 g (32.6 mmol) ofacrylic acid, 36.8 mg (0.296 mmol) of 4-methoxyphenol, and 284 mg (2.96mmol) of methanesulfonic acid, the mixture was refluxed for 10 hours.After completion of the reaction, the reaction mixture was cooled to 25°C., added to 300 ml of water, and extracted twice with 200 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (toluene:ethyl acetate=96:4) toobtain 5.94 g of an intermediate R1 as a white solid (yield: 57.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 8.87 (s, 1H), 6.69-6.74 (m, 2H),6.62-6.67 (m, 2H), 6.31 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.16 (dd, 1H,J=10.5 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.09 (t, 2H,J=6.5 Hz), 3.82 (t, 2H, J=6.5 Hz), 1.55-1.68 (m, 4H), 1.21-1.42 (m, 16H)

Step 3: Synthesis of Intermediate S1

A three-necked reactor equipped with a thermometer was charged with 6.20g (36.0 mmol) of trans-1,4-cyclohexanedicarboxylic acid, 40 ml of THF,and 8 ml of DMF under a nitrogen stream. After the addition of 2.06 g(18.0 mmol) of methanesulfonyl chloride to the mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 20° C. 1.99 g (19.6 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes while maintaining the temperatureof the reaction mixture at 20 to 30° C. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After the addition of 200 mg(1.64 mmol) of 4-(dimethylamino)pyridine and 5.70 g (16.4 mmol) of theintermediate R1 synthesized in the step 2 to the reaction mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. 1.99 g (19.6 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 250 ml of distilled water and 100 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 200 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (toluene:THF=95:5) to obtain 3.90 g of an intermediate S1as a white solid (yield: 47.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.1 (s, 1H), 6.96-7.01 (m, 2H),6.89-6.94 (m, 2H), 6.31 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.16 (dd, 1H,J=10.0 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz, 10.0 Hz), 4.09 (t, 2H,J=7.0 Hz), 3.93 (t, 2H, J=7.0 Hz), 2.18-2.26 (m, 1H), 2.04-2.10 (m, 2H),1.93-2.00 (m, 2H), 1.69 (tt, 2H, J=7.0 Hz, 7.0 Hz), 1.59 (tt, 2H, J=7.0Hz, 7.0 Hz), 1.20-1.52 (m, 21H)

Step 4: Synthesis of Intermediate T1

A three-necked reactor equipped with a thermometer was charged with 2.80g (5.58 mmol) of the intermediate S1 synthesized in the step 3 and 40 mlof THF under a nitrogen stream to prepare a solution. After the additionof 664 mg (5.80 mmol) of methanesulfonyl chloride to the solution, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 20° C. 586 mg (5.80 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. After theaddition of 56.6 mg (0.464 mmol) of 4-(dimethylamino)pyridine and 320 mg(2.32 mmol) of 2,5-dihydroxybenzaldehyde to the reaction mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. 586 mg (5.80 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes while maintaining thetemperature of the reaction mixture at 20 to 30° C. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 300 ml of distilled water and 50 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 150 ml of chloroform. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the resulting solid was dissolved in 20 ml of THF. 200ml of methanol was added to the solution to precipitate crystals. Thecrystals were filtered off, washed with methanol, and dried under vacuumto obtain 1.84 g of an intermediate T1 as a white solid (yield: 71.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.1 (s, 1H), 7.61 (d, 1H, J=2.8Hz), 7.37 (dd, 1H, J=2.8 Hz, 9.0 Hz), 7.20 (d, 1H, J=9.0 Hz), 6.94-7.01(m, 4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd,2H, J=10.5 Hz, 17.5 Hz), 5.81 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.15 (t, 4H,J=6.5 Hz), 3.93 (t, 4H, J=6.5 Hz), 2.54-2.75 (m, 4H), 2.24-2.39 (m, 8H),1.62-1.81 (m, 14H), 1.24-1.48 (m, 34H)

Step 5: Synthesis of Compound 31

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.36 mmol) of the intermediate T1 synthesized in the step 4, 375 mg(1.51 mmol) of the intermediate J synthesized in the step 1 of Example 4(see “Synthesis of compound 4”), 35.1 mg (0.151 mmol) of(±)-10-camphorsulfonic acid, 24 ml of THF, and 6 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (chloroform:THF=97:3) toobtain 1.54 g of a compound 31 as a light yellow solid (yield: 84.6%).

The structure of the target product was identified by ¹H-NMR.

1H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=2.0 Hz), 7.65-7.71(m, 3H), 7.34 (ddd, 1H, J=1.0 Hz, 8.0 Hz, 8.0 Hz), 7.17 (ddd, 1H, J=1.0Hz, 8.0 Hz, 8.0 Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.86-6.91 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.81 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.30 (t, 2H, J=7.0 Hz), 4.15 (t,4H, J=7.0 Hz), 3.94 (t, 4H, J=7.0 Hz), 2.54-2.73 (m, 4H), 2.25-2.39 (m,8H), 1.63-1.81 (m, 16H), 1.23-1.44 (m, 40H), 0.90 (t, 3H, J=7.0 Hz)

Example 45 Synthesis of Compound 32

Step 1: Synthesis of Intermediate U1

A three-necked reactor equipped with a thermometer was charged with15.00 g (87.12 mmol) of cis-1,4-cyclohexanedicarboxylic acid and 150 mlof THF under a nitrogen stream. After the addition of 5.48 g (47.92mmol) of methanesulfonyl chloride to the mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. After the addition of 5.07 g (50.09 mmol) oftriethylamine dropwise to the reaction mixture over 10 minutes, themixture was stirred at 25° C. for 2 hours. After the addition of 0.53 g(4.36 mmol) of 4-(dimethylamino)pyridine and 11.51 g (43.56 mmol) of4-(6-acryloyloxyhex-1-yloxy)phenol to the reaction mixture, the reactorwas immersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 5.29 g (52.27 mmol) of triethylamine was addeddropwise to the reaction mixture over 10 minutes. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 1000 ml of distilled water and 100 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 400 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The reaction mixture was concentrated using arotary evaporator, and the concentrate was purified by silica gel columnchromatography (THF:chloroform=5:95) to obtain 9.66 g of an intermediateU1 as a white solid (yield: 53%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 12.16 (s, 1H), 6.99 (d, 2H, J=9.0Hz), 6.92 (d, 2H, J=9.0 Hz), 6.32 (dd, 1H, J=0.5 Hz, 17.5 Hz), 6.17 (dd,1H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 1H, J=1.5 Hz, 10.0 Hz), 4.11 (t, 2H,J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.71-2.79 (m, 1H), 2.41-2.48 (m, 1H),1.57-1.91 (m, 12H), 1.34-1.50 (m, 4H)

Step 2: Synthesis of Intermediate V1

A three-necked reactor equipped with a thermometer was charged with 2.50g (5.97 mmol) of the intermediate U1 synthesized in the step 1 and 30 mlof THF under a nitrogen stream to prepare a solution. After the additionof 0.70 g (6.10 mmol) of methanesulfonyl chloride to the solution, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. After the addition of 0.63 g (6.22 mmol) oftriethylamine dropwise to the reaction mixture over 5 minutes, themixture was stirred at 25° C. for 2 hours. After the addition of 0.06 g(0.50 mmol) of 4-(dimethylamino)pyridine and 0.34 g (2.49 mmol) of2,5-dihydroxybenzaldehyde to the reaction mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 0.60 g (5.97 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After completion of thereaction, 200 ml of distilled water and 20 ml of a saturated sodiumchloride solution were added to the reaction mixture, followed byextraction twice with 100 ml of chloroform. The organic layer was driedover anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator.After the addition of 100 ml of toluene to the concentrate, an insolublesolid was filtered off. The solid was washed with methanol, and driedunder vacuum to obtain 1.32 g of an intermediate V1 as a white solid(yield: 56%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.02 (s, 1H), 7.67 (d, 1H, J=3.0Hz), 7.55 (dd, 1H, J=3.0 Hz, 8.5 Hz), 7.39 (d, 1H, J=8.5 Hz), 7.01 (d,4H, J=9.0 Hz), 6.93 (d, 4H, J=9.0 Hz), 6.31 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.17 (dd, 2H, J=10.0 Hz, 17.5 Hz), 5.93 (dd, 2H, J=1.5 Hz, 10.0 Hz),4.11 (t, 4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 2.78-3.02 (m, 4H),1.79-2.05 (m, 16H), 1.55-1.76 (m, 8H), 1.33-1.49 (m, 8H)

Step 3: Synthesis of Compound 32

A three-necked reactor equipped with a thermometer was charged with 1.20g (1.28 mmol) of the intermediate V1 synthesized in the step 2 and 30 mlof THF under a nitrogen stream to prepare a solution. After the additionof 0.26 ml (0.26 mmol) of 1 N hydrochloric acid and 0.48 g (1.92 mmol)of the intermediate J synthesized in the step 1 of Example 4 (see“Synthesis of compound 4”) to the solution, the mixture was stirred at40° C. for 7 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=98:2)to obtain 1.23 g of a compound 32 as a light yellow solid (yield: 82%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=2.5 Hz), 7.68 (s,1H), 7.64 (d, 1H, J=8.0 Hz), 7.58 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.31 (dt,1H, J=1.0 Hz, 7.5 Hz), 7.05-7.14 (m, 3H), 6.98 (d, 2H, J=9.0 Hz), 6.96(d, 2H, J=9.0 Hz), 6.86 (d, 2H, J=9.0 Hz), 6.84 (d, 2H, J=9.0 Hz), 6.39(dd, 1H, J=1.5 Hz, 17.5 Hz), 6.39 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.12 (dd,1H, J=10.5 Hz, 17.5 Hz), 6.12 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.81 (dd,1H, J=1.5 Hz, 10.5 Hz), 5.81 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.28 (t, 2H,J=7.5 Hz), 4.17 (t, 2H, J=6.5 Hz), 4.16 (t, 2H, J=6.5 Hz), 3.87-3.96 (m,4H), 2.75-2.90 (m, 4H), 2.08-2.26 (m, 8H), 1.85-2.03 (m, 8H), 1.65-1.82(m, 10H), 1.24-1.54 (m, 14H), 0.87 (t, 3H, J=7.0 Hz)

Example 46 Synthesis of Compound 33

Step 1: Synthesis of Intermediate W1

A three-necked reactor equipped with a thermometer was charged with 1.50g (3.58 mmol) of the intermediate A synthesized in the step 1 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.43 g (3.76 mmol)of methanesulfonyl chloride to the solution, the reactor was immersed ina water bath to adjust the temperature of the reaction mixture to 15° C.After the addition of 0.40 g (3.94 mmol) of triethylamine dropwise tothe reaction mixture over 5 minutes, the mixture was stirred at 25° C.for 2 hours. After the addition of 2.48 g (17.92 mmol) of2,5-dihydroxybenzaldehyde and 0.04 g (0.36 mmol) of4-(dimethylamino)pyridine to the reaction mixture, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 0.44 g (4.30 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After completion of thereaction, 300 ml of distilled water and 50 ml of a saturated sodiumchloride solution were added to the reaction mixture, followed byextraction twice with 100 ml of ethyl acetate. The organic layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator.After the addition of 100 ml of toluene to the concentrate, an insolublesolid was removed by filtration. The filtrate was concentrated using arotary evaporator, and the concentrate was purified by silica gel columnchromatography (THF:toluene=5:95) to obtain 0.80 g of an intermediate W1as a white solid (yield: 41%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.91 (s, 1H), 9.86 (s, 1H), 7.32(d, 1H, J=3.0 Hz), 7.25 (dd, 1H, J=3.0 Hz, 9.0 Hz), 7.01 (d, 1H, J=9.0Hz), 6.97 (d, 2H, J=9.0 Hz), 6.87 (d, 2H, J=9.0 Hz), 6.40 (dd, 1H, J=1.5Hz, 17.5 Hz), 6.12 (dd, 1H, J=10.0 Hz, 17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz,10.0 Hz), 4.17 (t, 2H, J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.53-2.65 (m,2H), 2.23-2.35 (m, 4H), 1.75-1.84 (m, 2H), 1.62-1.75 (m, 6H), 1.41-1.55(m, 4H)

Step 2: Synthesis of Intermediate X1

A three-necked reactor equipped with a thermometer was charged with 0.87g (2.09 mmol) of the intermediate U1 synthesized in the step 1 ofExample 45 (see “Synthesis of compound 32”) and 30 ml of THF under anitrogen stream to prepare a solution. After the addition of 0.25 g(2.16 mmol) of methanesulfonyl chloride to the solution, the reactor wasimmersed in a water bath to adjust the temperature of the reactionmixture to 15° C. 0.23 g (2.23 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes. After the dropwise addition, themixture was stirred at 25° C. for 2 hours. After the addition of 0.02 g(0.14 mmol) of 4-(dimethylamino)pyridine and 0.75 g (1.39 mmol) of theintermediate W1 synthesized in the step 1 to the reaction mixture, thereactor was immersed in a water bath to adjust the temperature of thereaction mixture to 15° C. 0.17 g (1.67 mmol) of triethylamine was addeddropwise to the reaction mixture over 5 minutes. After the dropwiseaddition, the mixture was stirred at 25° C. for 2 hours. Aftercompletion of the reaction, 200 ml of distilled water and 20 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 100 ml of chloroform. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator. After the addition of 100 ml of toluene to the concentrate,an insoluble solid was filtered off. The solid was washed with methanol,and dried under vacuum to obtain 0.98 g of an intermediate X1 as a whitesolid (yield: 75%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.09 (s, 1H), 7.61 (d, 1H, J=3.0Hz), 7.36 (dd, 1H, J=3.0 Hz, 9.0 Hz), 7.21 (d, 1H, J=9.0 Hz), 6.97 (d,2H, J=9.0 Hz), 6.97 (d, 2H, J=9.0 Hz), 6.87 (d, 2H, J=9.0 Hz), 6.87 (d,2H, J=9.0 Hz), 6.40 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.40 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.12 (dd, 1H, J=10.0 Hz, 17.5 Hz), 6.12 (dd, 1H, J=10.0 Hz,17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.0 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.0Hz), 4.17 (t, 2H, J=6.5 Hz), 4.17 (t, 2H, J=6.5 Hz), 3.94 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5 Hz), 2.77-2.93 (m, 2H), 2.52-2.66 (m, 2H),2.09-2.37 (m, 8H), 1.85-2.04 (m, 4H), 1.58-1.84 (m, 12H), 1.38-1.56 (m,8H)

Step 3: Synthesis of Compound 33

A three-necked reactor equipped with a thermometer was charged with 0.94g (1.00 mmol) of the intermediate X1 synthesized in the step 2 and 15 mlof THF under a nitrogen stream to prepare a solution. After the additionof 0.20 ml (0.20 mmol) of 1 N hydrochloric acid and 0.37 g (1.49 mmol)of the intermediate J synthesized in the step 1 of Example 4 (see“Synthesis of compound 4”) to the solution, the mixture was stirred at60° C. for 10 hours, After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=98:2)to obtain 0.92 g of a compound 33 as a light yellow solid (yield: 79%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=2.5 Hz), 7.64-7.71(m, 3H), 7.33 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.07-7.19 (m, 3H), 6.99 (d,2H, J=9.0 Hz), 6.96 (d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz), 6.87 (d,2H, J=9.0 Hz), 6.40 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.39 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 6.11 (dd, 1H, J=10.5 Hz,17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 5.81 (dd, 1H, J=1.5 Hz, 10.5Hz), 4.28 (t, 2H, J=7.5 Hz), 4.17 (t, 2H, J=6.5 Hz), 4.16 (t, 2H, J=6.5Hz), 3.90-3.97 (m, 4H), 2.80-2.88 (m, 2H), 2.54-2.71 (m, 2H), 2.26-2.38(m, 4H), 2.09-2.26 (m, 4H), 1.85-2.03 (m, 4H), 1.64-1.83 (m, 14H),1.24-1.55 (m, 14H), 0.87 (t, 3H, J=7.0 Hz)

Phase Transition Temperature Measurement 2

10 mg of the compound (compounds 9 to 33) was weighed, and placed in asolid state between two glass substrates provided with a polyimidealignment film subjected to a rubbing treatment. The substrates wereplaced on a hot plate, heated from 40° C. to 250° C., and cooled to 40°C. A change in structure when the temperature was changed was observedusing a polarizing microscope.

The phase transition temperature measurement results are shown in Table3.

TABLE 3 Compound No. Phase transition temperature Example 22 Compound  9

Example 23 Compound 10

Example 24 Compound 11

Example 25 Compound 12

Example 26 Compound 13

Example 27 Compound 14

Example 28 Compound 15

Example 29 Compound 16

Example 30 Compound 17

Example 31 Compound 18

Example 32 Compound 19

Example 33 Compound 20

Example 34 Compound 21

Example 35 Compound 22

Example 36 Compound 23

Example 37 Compound 24

Example 38 Compound 25

Example 39 Compound 26

Example 40 Compound 27

Example 41 Compound 28

Example 42 Compound 29

Example 43 Compound 30

Example 44 Compound 31

Example 45 Compound 32

Example 46 Compound 33

Examples 47 and 48

1.0 g of the compound 9 obtained in Example 22 or the compound 10obtained in Example 23, 30 mg of the photoinitiator A, and 100 mg of a1% cyclopentanone solution of the surfactant A were dissolved in 2.3 gof cyclopentanone and 2.26 g of chloroform. The solution was filteredthrough a disposable filter having a pore size of 0.45 μm to obtain apolymerizable composition (polymerizable compositions 14 and 15).

Example 49

1.0 g of the compound 11 obtained in Example 24, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 16.

Example 50

1.0 g of the compound 12 obtained in Example 25, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone and 1.7 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 17.

Example 51

1.0 g of the compound 13 obtained in Example 26, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 18.

Example 52

1.0 g of the compound 14 obtained in Example 27, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone and 1.7 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 19.

Examples 53 and 54

1.0 g of the compound 15 obtained in Example 28 or the compound 16obtained in Example 29, 30 mg of the photoinitiator A, and 100 mg of a1% cyclopentanone solution of the surfactant A were dissolved in 2.3 gof cyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 20 and 21).

Example 55

0.5 g of the compound 17 obtained in Example 30, 0.5 g of the compound 4obtained in Example 4, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 3.26 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 22.

Examples 56 to 63

1.0 g of each of the compounds 18 to 25 respectively obtained inExamples 31 to 38, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 23 to 30).

Example 64

1.0 g of the compound 26 obtained in Example 39, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone and 0.7 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 m to obtain a polymerizable composition 31.

Example 65

1.0 g of the compound 27 obtained in Example 40, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 32.

Example 66

1.0 g of the compound 28 obtained in Example 41, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone and 0.7 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 33.

Examples 67 and 68

1.0 g of the compound 29 obtained in Example 42 or the compound 30obtained in Example 43, 30 mg of the photoinitiator A, and 100 mg of a1% cyclopentanone solution of the surfactant A were dissolved in 2.3 gof cyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 m to obtain a polymerizable composition(polymerizable compositions 34 and 35).

Example 69

1.0 g of the compound 31 obtained in Example 44, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone and 0.7 g ofchloroform. The solution was filtered through a disposable filter havinga pore size of 0.45 μm to obtain a polymerizable composition 36.

Examples 70 and 71

1.0 g of the compound 32 obtained in Example 44 or the compound 33obtained in Example 45, 30 mg of the photoinitiator A, and 100 mg of a1% cyclopentanone solution of the surfactant A were dissolved in 2.3 gof cyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 37 and 38).

The polymerizable compositions 14 to 38 were polymerized by thefollowing method to obtain polymers. The retardation was measured, andthe wavelength dispersion was evaluated using the resulting polymers.

Retardation Measurement and Wavelength Dispersion Evaluation II (i)Formation 1 of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 16 to 18, 20 to 30, 32, and 34 to38 was applied to a transparent glass substrate provided with apolyimide alignment film subjected to a rubbing treatment using a #4wire bar. The resulting film was dried for 1 minute at the temperatureshown in Table 4, and subjected to an alignment treatment for 1 minuteat the temperature shown in Table 4 to form a liquid crystal layer. UVrays were applied to the liquid crystal layer at a dose of 2000 mJ/cm²at the temperature shown in Table 4 to effect polymerization to preparea wavelength dispersion measurement sample.

(ii) Formation 2 of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 14, 15, 19, 31, and 33 wasapplied to a transparent glass substrate provided with a polyimidealignment film subjected to a rubbing treatment using a #6 wire bar. Theresulting film was dried for 1 minute at the temperature shown in Table4, and subjected to an alignment treatment for 1 minute at thetemperature shown in Table 4 to form a liquid crystal layer. UV rayswere applied to the liquid crystal layer at a dose of 2000 mJ/cm² at thetemperature shown in Table 4 to effect polymerization to prepare awavelength dispersion measurement sample.

(iii) Retardation Measurement and Wavelength Dispersion Evaluation

The retardation was measured, and the wavelength dispersion wasevaluated in the same manner as described above using the resultingsamples.

Table 4 shows the thickness (μm) of the liquid crystal polymer filmsobtained by polymerizing the polymerizable compositions, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

TABLE 4 Polymer- Polymerizable Polymerizable Alignment izable compoundcompound Drying treatment Exposure Thick- Re composi- Ratio Ratiotemperature temperature temperature ness (548.5 tion Type (%) Type (%)(° C.) (° C.) (° C.) (μm) nm) α β Example 47 14 Compound 9  100 — — 150115 115 1.697 117.28 0.617 1.076 Example 48 15 Compound 10 100 — — 14090 90 1.872 144.39 0.829 1.033 Example 49 16 Compound 11 100 — — 150 115115 1.537 129.10 0.874 0.997 Example 50 17 Compound 12 100 — — 145 105105 1.201 95.65 0.854 1.043 Example 51 18 Compound 13 100 — — 120 23 231.504 117.36 0.879 1.045 Example 52 19 Compound 14 100 — — 150 90 901.881 175.24 0.863 1.026 Example 53 20 Compound 15 100 — — 150 110 1101.490 137.54 0.858 1.028 Example 54 21 Compound 16 100 — — 175 23 231.477 115.05 0.787 1.031 Example 55 22 Compound 17 50 Compound 4 50 15023 23 1.818 69.40 0.972 0.995 Example 56 23 Compound 18 100 — — 120 2323 1.593 122.81 0.835 1.026 Example 57 24 Compound 19 100 — — 130 23 231.620 124.28 0.848 1.057 Example 58 25 Compound 20 100 — — 120 23 231.484 100.57 0.728 1.046 Example 59 26 Compound 21 100 — — 120 80 801.514 105.37 0.814 1.039 Example 60 27 Compound 22 100 — — 120 23 231.669 123.98 0.841 1.027 Example 61 28 Compound 23 100 — — 120 75 751.454 109.76 0.759 1.055 Example 62 29 Compound 24 100 — — 135 23 231.554 101.40 0.737 1.072 Example 63 30 Compound 25 100 — — 120 23 231.486 112.87 0.824 1.058 Example 64 31 Compound 26 100 — — 150 90 852.344 194.63 0.878 1.031 Example 65 32 Compound 27 100 — — 130 70 651.519 122.28 0.847 1.023 Example 66 33 Compound 28 100 — — 150 23 232.301 177.20 0.850 1.025 Example 67 34 Compound 29 100 — — 130 23 231.486 113.07 0.838 1.022 Example 68 35 Compound 30 100 — — 130 23 231.533 115.70 0.834 1.032 Example 69 36 Compound 31 100 — — 130 65 552.287 162.31 0.825 1.041 Example 70 37 Compound 32 30 Compound 4 70 13023 23 1.504 121.64 0.834 1.017 Example 71 38 Compound 33 30 Compound 470 130 23 23 1.616 111.36 0.827 1.047

As is clear from the results shown in Table 4, it was confirmed that thepolymers obtained in Examples 47 to 71 using the compounds 9 to 33according to the invention were an optically anisotropic article. Theoptically anisotropic articles showed ideal wideband wavelengthdispersion in which the value α was smaller than 1, and the value β waslarger than 1, or almost equal to 1.

Example 71 Compound 34

Step 1: Synthesis of Intermediate Y1

A four-necked reactor equipped with a thermometer was charged with 2.50g (15.1 mmol) of 2-hydrazinobenzothiazole and 20 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.38 g(22.7 mmol) of cesium carbonate and 2.45 g (18.2 mmol) of3-bromo-2-methyl-1-propene to the solution, the mixture was stirred at25° C. for 18 hours. After completion of the reaction, the reactionmixture was added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (hexane:ethyl acetate=80:20) to obtain368 mg of an intermediate Y1 as a white solid (yield: 11.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.59 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.52 (dd, 1H, J=1.5 Hz, 8.0 Hz), 7.26 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0Hz), 7.05 (ddd, 1H, J=1.5 Hz, 7.5 Hz, 8.0 Hz), 4.98 (s, 1H), 4.86 (s,1H), 4.29 (s, 2H), 4.12 (s, 2H), 1.71 (s, 3H)

Step 2: Synthesis of Compound 34

A four-necked reactor equipped with a thermometer was charged with 368mg (1.68 mmol) of the intermediate Y1 synthesized in the step 1, 1.00 g(1.06 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 15 ml of THF undera nitrogen stream to prepare a solution. After the addition of 49.2 mg(0.21 mmol) of (±)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.07 g of a compound 34 as a white solid(yield: 88.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (d, 1H, J=2.5 Hz), 7.70 (d,1H, J=7.5 Hz), 7.67 (d, 1H, J=8.0 Hz), 7.63 (s, 1H), 7.34 (dd, 1H, J=7.5Hz, 8.0 Hz), 7.18 (dd, 1H, J=7.5 Hz, 7.5 Hz), 7.12 (d, 1H, J=9.0 Hz),7.10 (dd, 1H, J=2.5 Hz, 9.0 Hz), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H,J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.40 (dd, 2H, J=0.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz),4.98 (s, 1H), 4.90 (s, 2H), 4.83 (s, 1H), 4.18 (t, 4H, J=6.5 Hz), 3.95(t, 4H, J=6.5 Hz), 2.56-2.66 (m, 4H), 2.31-2.36 (m, 8H), 1.76-1.82 (m,7H), 1.64-1.74 (m, 12H), 1.40-1.55 (m, 8H)

Example 73 Compound 35

Step 1: Synthesis of Intermediate Z1

A four-necked reactor equipped with a thermometer was charged with 5.00g (30.3 mmol) of 2-hydrazinobenzothiazole and 50 ml of DMF under anitrogen stream to prepare a solution. After the addition of 14.8 g(45.5 mmol) of cesium carbonate and 4.98 g (36.4 mmol) of4-bromo-2-methylpropane to the solution, the mixture was stirred at 25°C. for 24 hours. After completion of the reaction, the reaction mixturewas added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (n-hexane:ethyl acetate=85:15) toobtain 3.28 g of an intermediate Z1 as a white solid (yield: 48.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.52 (dd, 1H, J=1.0 Hz, 8.5 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.5Hz), 7.06 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 4.24 (s, 2H), 3.57 (d,2H, J=6.5 Hz), 2.14-2.25 (triplet of septets, 1H, J=6.5 Hz, 6.5 Hz),1.00 (d, 6H, J=6.5 Hz)

Step 2: Synthesis of Compound 35

A four-necked reactor equipped with a thermometer was charged with 518mg (2.34 mmol) of the intermediate Z1 synthesized in the step 1, 2.00 g(2.12 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 20 ml of THF undera nitrogen stream to prepare a solution. After the addition of 54.4 mg(0.24 mmol) of (±)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 7 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.83 g of a compound 35 as a white solid(yield: 75.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.76 (d, 1H, J=2.5 Hz), 7.692 (s,1H), 7.690 (d, 1H, J=7.5 Hz), 7.66 (d, 1H, J=8.0 Hz), 7.34 (dd, 1H,J=7.5 Hz, 8.0 Hz), 7.17 (dd, 1H, J=7.5 Hz, 7.5 Hz), 7.12 (d, 1H, J=9.0Hz), 7.10 (dd, 1H, J=2.5 Hz, 9.0 Hz), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d,2H, J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz),4.16-4.19 (m, 6H), 3.95 (t, 4H, J=6.5 Hz), 2.59-2.68 (m, 4H), 2.23-2.35(m, 9H), 1.76-1.82 (m, 4H), 1.66-1.74 (m, 12H), 1.42-1.54 (m, 8H), 1.03(d, 6H, J=6.5 Hz)

Example 74 Compound 36

Step 1: Synthesis of Intermediate A2

A four-necked reactor equipped with a thermometer was charged with 2.50g (15.1 mmol) of 2-hydrazinobenzothiazole and 20 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.38 g(22.7 mmol) of cesium carbonate and 4.17 g (18.2 mmol) of2-bromomethyl-1,4-benzodioxane to the solution, the mixture was stirredat 25° C. for 6 hours. After completion of the reaction, the reactionmixture was added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (n-hexane:ethyl acetate=70:30) toobtain 2.39 g of an intermediate A2 as a white solid (yield: 53.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.62 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.51 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.28 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0Hz), 7.08 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 8.0 Hz), 6.83-6.90 (m, 4H), 4.72(dddd, 1H, J=2.5 Hz, 3.0 Hz, 7.0 Hz, 7.0 Hz), 4.64 (s, 2H), 4.39 (dd,1H, J=2.5 Hz, 12.5 Hz), 4.25 (dd, 1H, J=3.0 Hz, 15.0 Hz), 4.07 (dd, 1H,J=7.0 Hz, 12.0 Hz), 3.98 (dd, 1H, J=7.0 Hz, 15.0 Hz)

Step 2: Synthesis of Compound 36

A four-necked reactor equipped with a thermometer was charged with 627mg (2.13 mmol) of the intermediate A2 synthesized in the step 1, 1.00 g(1.06 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 15 ml of THF undera nitrogen stream to prepare a solution. After the addition of 49.2 mg(0.21 mmol) of (±)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 4 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.11 g of a compound 36 as a white solid(yield: 84.8%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.02 (s, 1H), 7.76 (d, 1H, J=2.0Hz), 7.71 (d, 1H, J=7.5 Hz), 7.67 (d, 1H, J=8.0 Hz), 7.36 (dd, 1H, J=7.5Hz, 8.0 Hz), 7.20 (dd, 1H, J=7.5 Hz, 7.5 Hz), 7.13 (dd, 1H, J=2.0 Hz,9.0 Hz), 7.11 (d, 1H, J=9.0 Hz), 6.99 (d, 2H, J=9.0 Hz), 6.97 (d, 2H,J=9.0 Hz), 6.88 (d, 4H, J=9.0 Hz), 6.85-6.87 (m, 4H), 6.40 (dd, 2H,J=1.0 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H,J=1.0 Hz, 10.5 Hz), 4.75 (dd, 1H, J=6.0 Hz, 15.0 Hz), 4.68 (dddd, 1H,J=2.0 Hz, 5.5 Hz, 6.0 Hz, 7.0 Hz), 4.47 (dd, 1H, J=2.0 Hz, 11.5 Hz),4.42 (dd, 1H, J=5.5 Hz, 15.0 Hz), 4.18 (t, 4H, J=7.0 Hz), 4.08 (dd, 1H,J=7.5 Hz, 11.5 Hz), 3.95 (t, 4H, J=6.0 Hz), 2.57-2.68 (m, 3H), 2.41-2.47(m, 1H), 2.24-2.36 (m, 6H), 2.17-2.20 (m, 2H), 1.77-1.82 (m, 4H),1.69-1.74 (m, 8H), 1.56-1.65 (m, 4H), 1.42-1.54 (m, 8H)

Example 75 Compound 37

Step 1: Synthesis of Intermediate B2

A four-necked reactor equipped with a thermometer was charged with 5.00g (30.3 mmol) of 2-hydrazinobenzothiazole and 50 ml of DMF under anitrogen stream to prepare a solution. After the addition of 14.8 g(45.5 mmol) of cesium carbonate and 7.30 g (36.6 mmol) ofβ-bromophenetole to the solution, the mixture was stirred at 25° C. for24 hours. After completion of the reaction, the reaction mixture wasadded to 200 ml of water, and extracted with 300 ml of ethyl acetate.After drying the ethyl acetate layer over anhydrous sodium sulfate,sodium sulfate was separated by filtration. Ethyl acetate was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a yellow solid. The yellow solid was purified by silica gelcolumn chromatography (n-hexane:ethyl acetate=70:30) to obtain 2.26 g ofan intermediate B2 as a white solid (yield: 28.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.61 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.53 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.26-7.31 (m, 3H), 7.07 (ddd, 1H, J=1.0Hz, 7.5 Hz, 8.0 Hz), 6.97 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 6.90 (dd,2H, J=1.0 Hz, 8.5 Hz), 4.70 (s, 2H), 4.39 (t, 2H, J=4.5 Hz), 4.23 (t,2H, J=4.5 Hz)

Step 2: Synthesis of Compound 37

A four-necked reactor equipped with a thermometer was charged with 312mg (1.77 mmol) of the intermediate B2 synthesized in the step 1, 1.00 g(1.06 mmol) of the intermediate B synthesized in the step 2 of Example 1(see “Synthesis of compound 1”), 3 ml of ethanol, and 15 ml of THF undera nitrogen stream to prepare a solution. After the addition of 27.1 mg(0.12 mmol) of (±)-10-camphorsulfonic acid to the solution, the mixturewas stirred at 40° C. for 7 hours. After completion of the reaction, thereaction mixture was added to 150 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a yellow solid. The yellow solid waspurified by silica gel column chromatography (toluene:ethylacetate=90:10) to obtain 1.18 g of a compound 37 as a white solid(yield: 92.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.14 (s, 1H), 7.78 (d, 1H, J=1.0Hz), 7.70 (d, 1H, J=8.0 Hz), 7.67 (d, 1H, J=8.0 Hz), 7.35 (dd, 1H, J=7.5Hz, 8.0 Hz), 7.24-7.27 (m, 2H), 7.18 (dd, 1H, J=7.5 Hz, 8.0 Hz), 7.14(dd, 1H, J=1.0 Hz, 7.5 Hz), 7.12 (d, 1H, J=7.5 Hz), 6.93-7.00 (m, 5H),6.87-6.90 (m, 6H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.69 (t, 2H,J=6.0 Hz), 4.36 (t, 2H, J=6.0 Hz), 4.17 (t, 4H, J=6.5 Hz), 3.95 (t, 2H,J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz), 2.56-2.68 (m, 3H), 2.31-2.39 (m, 5H),2.23-2.27 (m, 2H), 2.11-2.14 (m, 2H), 1.77-1.85 (m, 4H), 1.69-1.74 (m,8H), 1.42-1.65 (m, 12H)

Example 76 Compound 38

Step 1: Synthesis of Intermediate C2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mmol) of cesium carbonate and 3.15 g (14.5 mmol) of2-bromoethylphenyl sulfide to the solution, the mixture was stirred at25° C. for 3 hours. After completion of the reaction, the reactionmixture was added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a yellow solid. The yellow solid was purified bysilica gel column chromatography (n-hexane:ethyl acetate=80:20) toobtain 1.55 g of an intermediate C2 as a white solid (yield: 42.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.61 (dd, 1H, J=1.3 Hz, 8.0 Hz),7.53 (dd, 1H, J=1.3 Hz, 8.0 Hz), 7.38-7.43 (m, 2H), 7.27-7.32 (m, 3H),7.21 (ddd, 1H, J=1.3 Hz, 8.0 Hz, 8.0 Hz), 7.08 (ddd, 1H, J=1.3 Hz, 8.0Hz, 8.0 Hz), 4.44 (s, 2H), 4.00 (t, 2H, J=6.5 Hz), 3.36 (t, 2H, J=6.5Hz)

Step 2: Synthesis of Compound 38

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 534 mg (1.78 mmol) of theintermediate C2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.67 g of a compound 38 as a light yellow solid (yield:86.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74 (s, 1H), 7.65-7.72 (m, 3H),7.44-7.49 (m, 2H), 7.30-7.39 (m, 3H), 7.23 (ddd, 1H, J=1.0 Hz, 7.0 Hz,7.0 Hz), 7.19 (ddd, 1H, J=1.0 Hz, 7.0 Hz, 7.0 Hz), 7.10-7.14 (m, 2H),6.96-7.01 (m, 4H), 6.86-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz),5.22 (t, 2H, J=8.0 Hz), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz),3.28 (t, 2H, J=8.0 Hz), 2.52-2.73 (m, 4H), 2.24-2.40 (m, 8H), 1.62-1.84(m, 16H), 1.41-1.56 (m, 8H)

Example 77 Compound 39

Step 1: Synthesis of Intermediate D2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 2.83 g (14.5 mmol) of2-(2-bromoethyl)-1,3-dioxane to the mixture over 5 minutes, the mixturewas stirred at 25° C. for 25 hours. After completion of the reaction,200 ml of water was added to the reaction mixture, followed byextraction twice with 100 ml of ethyl acetate. The organic layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator, andthe resulting white solid was washed with 50 ml of toluene, and driedunder vacuum to obtain 1.45 g of an intermediate D2 as a white solid(yield: 42.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (400 MHz, CDCl₃, TMS, δ ppm): 7.59 (dd, 1H, J=1.3 Hz, 7.5 Hz),7.52 (dd, 1H, J=1.3 Hz, 7.5 Hz), 7.27 (ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5Hz), 7.05 (ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5 Hz), 4.70 (t, 1H, J=4.5 Hz),4.47 (s, 2H), 4.00-4.12 (m, 2H), 3.93 (t, 2H, J=6.5 Hz), 3.68-3.76 (m,2H), 1.98-2.11 (m, 3H), 1.29-1.36 (m, 1H)

Step 2: Synthesis of Compound 39

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 495 mg (1.78 mmol) of theintermediate D2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 3 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=92:8) to obtain 1.61 g of a compound 39 as a light yellow solid(yield: 83.8%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.79 (s, 1H), 7.74 (d, 1H, J=1.5Hz), 7.69 (dd, 1H, J=1.3 Hz, 6.5 Hz), 7.67 (dd, 1H, J=1.3 Hz, 6.5 Hz),7.34 (ddd, 1H, J=1.3 Hz, 6.5 Hz, 6.5 Hz), 7.16 (ddd, 1H, J=1.3 Hz, 6.5Hz, 6.5 Hz), 7.08-7.13 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m, 4H),6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz),5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.68 (t, 1H, J=5.0 Hz), 4.41 (t, 2H,J=7.5 Hz), 4.18 (t, 4H, J=6.5 Hz), 4.07-4.14 (m, 2H), 3.94 (t, 4H, J=6.5Hz), 3.71-3.79 (m, 2H), 2.55-2.75 (m, 4H), 2.25-2.41 (m, 8H), 2.01-2.15(m, 3H), 1.64-1.84 (m, 16H), 1.41-1.56 (m, 8H), 1.32-1.38 (m, 1H)

Example 78 Compound 40

Step 1: Synthesis of Intermediate E2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. After the addition of 2.42 g (14.5 mmol) of2-bromomethyl-1,3-dioxolane to the mixture over 5 minutes, the mixturewas stirred at 25° C. for 3 hours. After completion of the reaction, 200ml of water was added to the reaction mixture, followed by extractiontwice with 100 ml of ethyl acetate. The organic layer was dried overanhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator, andthe concentrate was purified by silica gel column chromatography(n-hexane:ethyl acetate=55:45) to obtain 1.31 g of an intermediate E2 asa white solid (yield: 43.1%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.53 (dd, 1H, J=1.0 Hz, 7.5 Hz), 7.27 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5Hz), 7.06 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 5.19 (t, 1H, J=4.5 Hz),4.63 (s, 2H), 3.93-4.05 (m, 4H), 3.86-3.94 (m, 2H)

Step 2: Synthesis of Compound 40

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 447 mg (1.78 mmol) of theintermediate E2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over sodium sulfate, andconcentrated using a rotary evaporator. The concentrate was purified bysilica gel column chromatography (toluene:ethyl acetate=85:15) to obtain1.60 g of a compound 40 as a light yellow solid (yield: 85.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz. CDCl₃. TMS. δ ppm): 8.11 (s. 1H). 7.76 (d. 1H. J=1.5Hz). 7.71 (dd. 1H. J=1.0 Hz, 7.5 Hz). 7.69 (dd. 1H. J=1.0 Hz. 7.5 Hz).7.39 (ddd. 1H. J=1.0 Hz. 7.5 Hz. 7.5 Hz). 7.17 (ddd. 1H. J=1.0 Hz, 7.5Hz. 7.5 Hz). 7.09-7.13 (m. 2H). 6.96-7.01 (m, 4H). 6.86-6.91 (m. 4H).6.40 (dd. 2H. J=1.5 Hz. 17.5 Hz). 6.13 (dd. 2H. J=10.5 Hz. 17.5 Hz).5.82 (dd. 2H, J=1.5 Hz. 10.5 Hz). 5.24 (t. 1H. J=3.5 Hz). 4.57 (d. 2H.J=3.5 Hz). 4.18 (t. 4H. J=6.5 Hz). 3.97-4.01 (m. 2H). 3.95 (t. 4H. J=6.5Hz). 3.86-3.90 (m. 2H). 2.55-2.74 (m. 4H). 2.25-2.41 (m. 8H). 1.64-1.84(m. 16H). 1.40-1.55 (m. 8H)

Example 79 Compound 41

Step 1: Synthesis of Intermediate F2

A four-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mmol) of cesium carbonate and 5.00 g (14.5 mmol) of2-(nonafluorobutyl)ethyl iodide to the solution, the mixture was stirredat 25° C. for 20 hours. After completion of the reaction, the reactionmixture was added to 200 ml of water, and extracted with 300 ml of ethylacetate. After drying the ethyl acetate layer over anhydrous sodiumsulfate, sodium sulfate was separated by filtration. Ethyl acetate wasevaporated from the filtrate under reduced pressure using a rotaryevaporator to obtain a brown solid. The brown solid was purified bysilica gel column chromatography (n-hexane:ethyl acetate=9:1) to obtain1.15 g of an intermediate F2 as a white solid (yield: 22.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.63 (dd, 1H, J=1.0 Hz, 7.5 Hz),7.57 (dd, 1H, J=1.0 Hz, 7.5 Hz), 7.32 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5Hz), 7.11 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 4.35 (s, 2H), 4.08 (t,2H, J=7.5 Hz), 2.56-2.70 (m, 2H)

Step 2: Synthesis of Compound 41

A three-necked reactor equipped with a thermometer was charged with 1.35g (1.44 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 654 mg (1.59 mmol) of theintermediate F2 synthesized in the step 1, 38.4 mg (0.165 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=92:8) to obtain 1.41 g of a compound 41 as a light yellow solid(yield: 73.6%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.74-7.78 (m, 2H), 7.69-7.73 (m,2H), 7.38 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 7.21 (ddd, 1H, J=1.0 Hz,7.5 Hz, 7.5 Hz), 7.11-7.17 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.0 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.0 Hz), 4.61-4.69 (m, 2H), 4.18 (t, 4H,J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.52-2.71 (m, 6H), 2.25-2.40 (m, 8H),1.61-1.84 (m, 16H), 1.41-1.55 (m, 8H)

Example 80 Compound 42

Step 1: Synthesis of Intermediate G2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.11 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.89 g(24.21 mmol) of cesium carbonate and 1.95 g (14.53 mmol) of3-bromopropionitrile to the solution, the mixture was stirred at 25° C.for 15 hours. After completion of the reaction, 500 ml of distilledwater was added to the reaction mixture, followed by extraction twicewith 100 ml of ethyl acetate. The organic layer was dried over anhydroussodium sulfate, and sodium sulfate was separated by filtration. Thefiltrate was concentrated using a rotary evaporator. After the additionof 20 ml of toluene to the concentrate, the mixture was cooled to 0° C.to precipitate crystals. The crystals were filtered off, and dried undervacuum to obtain 1.12 g of an intermediate G2 as a white solid (yield:42%).

The structure of the target product was identified by ¹H-NMR,

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.70 (dd, 111, J=1.0 Hz, 8.0 Hz),7.42 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.24 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.03(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.47 (s, 2H), 3.99 (t, 2H, J=6.5 Hz), 2.97(t, 2H, J=6.5 Hz)

Step 2: Synthesis of Compound 42

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.44 ml (0.44 mmol)of 1 N hydrochloric acid and 1.12 g (5.13 mmol) of the intermediate G2synthesized in the step 1 to the solution, the mixture was stirred at60° C. for 20 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 0.55 g of a compound 42 as a light yellow solid (yield: 91%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.84 (s, 1H), 7.66-7.76 (m, 3H),7.38 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.22 (dt, 1H, J=1.0 Hz, 7.5 Hz),7.13-7.16 (m, 2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88(d, 2H, J=9.0 Hz), 6.87 (d, 2H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5Hz), 4.62 (t, 2H, J=7.0 Hz), 4.17 (t, 4H, J=6.5 Hz), 3.94 (t, 2H, J=6.5Hz), 3.94 (t, 2H, J=6.5 Hz), 2.85 (t, 2H, J=7.0 Hz), 2.70-2.80 (m, 1H),2.54-2.70 (m, 3H), 2.25-2.41 (m, 8H), 1.64-1.85 (m, 16H), 1.41-1.55 (m,8H)

Example 81 Compound 43

Step 1: Synthesis of Intermediate H2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.11 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.89 g(24.21 mmol) of cesium carbonate and 2.15 g (14.53 mmol) of3-bromobutyronitrile to the solution, the mixture was stirred at 25° C.for 15 hours. After completion of the reaction, 500 ml of distilledwater was added to the reaction mixture, followed by extraction twicewith 100 ml of ethyl acetate. The organic layer was dried over anhydroussodium sulfate, and sodium sulfate was separated by filtration. Thefiltrate was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (THF:toluene=1:9) toobtain 2.03 g of an intermediate H2 as a white solid (yield: 72%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.70 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.41 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.24 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.03(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.24 (s, 2H), 4.86-4.96 (m, 1H), 2.80-2.96(m, 2H), 1.27 (d, 3H, J=6.5 Hz)

Step 2: Synthesis of Compound 43

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.44 ml (0.44 mmol)of 1 N hydrochloric acid and 0.74 g (3.20 mmol) of the intermediate H2synthesized in the step 1 to the solution, the mixture was stirred at60° C. for 15 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.04 g of a compound 43 as a light yellow solid (yield: 85%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.18 (s, 1H), 7.65-7.76 (m, 3H),7.37 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.21 (dt, 1H, J=1.0 Hz, 7.5 Hz),7.13-7.16 (m, 2H), 6.98 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88(d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5Hz), 4.85-4.94 (m, 1H), 4.17 (t, 4H, J=6.5 Hz), 3.94 (t, 2H, J=6.5 Hz),3.94 (t, 2H, J=6.5 Hz), 3.28-3.46 (m, 2H), 2.53-2.80 (m, 4H), 2.23-2.41(m, 8H), 1.64-1.84 (m, 19H), 1.41-1.55 (m, 8H)

Example 82 Compound 44

Step 1: Synthesis of Intermediate 12

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.11 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.89 g(24.21 mmol) of cesium carbonate and 1.73 g (14.53 mmol) of propargylbromide to the solution, the mixture was stirred at 25° C. for 15 hours.After completion of the reaction, 500 ml of distilled water was added tothe reaction mixture, followed by extraction twice with 100 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (THF:toluene=1:19) to obtain 0.69 gof an intermediate 12 as a white solid (yield: 28%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.73 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.44 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.26 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.06(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.31 (s, 2H), 4.52 (d, 2H, J=2.5 Hz), 3.35(t, 1H, J=2.5 Hz)

Step 2: Synthesis of Compound 44

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.44 ml (0.44 mmol)of 1 N hydrochloric acid and 0.64 g (3.20 mmol) of the intermediate 12synthesized in the step 1 to the solution, the mixture was stirred at50° C. for 15 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.10 g of a compound 44 as a light yellow solid (yield: 92%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.92 (s, 1H), 7.67-7.78 (m, 3H),7.36 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.20 (dt, 1H, J=1.0 Hz, 7.5 Hz),7.11-7.17 (m, 2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88(d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5Hz), 5.14 (d, 2H, J=2.0 Hz), 4.17 (t, 4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5Hz), 2.54-2.76 (m, 4H), 2.24-2.42 (m, 9H), 1.64-1.84 (m, 16H), 1.41-1.56(m, 8H)

Example 83 Compound 45

Step 1: Synthesis of Intermediate J2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.11 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.89 g(24.21 mmol) of cesium carbonate and 1.93 g (14.53 mmol)4-bromo-1-butyne to the solution, the mixture was stirred at 25° C. for15 hours. The reaction mixture was heated to 60° C., and stirred for 3hours. After completion of the reaction, 500 ml of distilled water wasadded to the reaction mixture, followed by extraction twice with 100 mlof ethyl acetate. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (THF:toluene=1:19) toobtain 0.98 g of an intermediate J2 as a white solid (yield: 37%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.68 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.39 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.22 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.01(dt, 1H, J=1.0 Hz, 7.5 Hz), 5.33-5.40 (m, 1H), 5.29 (s, 2H), 4.91-4.97(m, 2H), 4.32-4.37 (m, 2H)

Step 2: Synthesis of Compound 45

A three-necked reactor equipped with a thermometer was charged with 1.00g (1.06 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”) and 30 ml of THF under a nitrogenstream to prepare a solution. After the addition of 0.44 ml (0.44 mmol)of 1 N hydrochloric acid and 0.7 g (3.20 mmol) of the intermediate J2synthesized in the step 1 to the solution, the mixture was stirred at50° C. for 15 hours. After completion of the reaction, the reactionmixture was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (chloroform:THF=40:1)to obtain 1.08 g of a compound 45 as a light yellow solid (yield: 89%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.76 (s, 1H), 7.66-7.76 (m, 3H),7.35 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.18 (dt, 1H, J=1.0 Hz, 7.5 Hz),7.09-7.13 (m, 2H), 6.99 (d, 2H, J=9.0 Hz), 6.98 (d, 2H, J=9.0 Hz), 6.88(d, 4H, J=9.0 Hz), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.5 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.19-5.27 (m,1H), 4.93-4.99 (m, 2H), 4.83-4.89 (m, 2H), 4.18 (t, 4H, J=6.5 Hz), 3.95(t, 4H, J=6.5 Hz), 2.54-2.74 (m, 4H), 2.24-2.40 (m, 8H), 1.63-1.84 (m,16H), 1.41-1.56 (m, 8H)

Example 84 Compound 46

Step 1: Synthesis of Intermediate K2

A three-necked reactor equipped with a thermometer was charged with 10.0g (72.4 mmol) of 2,5-dihydroxybenzaldehyde and 200 ml of dichloromethaneunder a nitrogen stream to prepare a solution. The solution was cooledto 0° C. After the addition of 35.06 g (0.27 mol) ofdiisopropylethylamine to the solution, 23.32 g (0.29 mmol) ofchloromethyl methyl ether was added to the mixture over 10 minutes.After the dropwise addition, the reaction mixture was heated to 25° C.,and stirred for 15 hours. After completion of the reaction, 1000 ml ofdistilled water was added to the reaction mixture, followed byextraction twice with 200 ml of dichloromethane. The organic layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator, andthe concentrate was purified by silica gel column chromatography(THF:toluene=1:19) to obtain 13.26 g of an intermediate K2 as acolorless oil (yield: 81%).

The structure of the target product was identified by ¹H-NMR. 15 [0697]

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 10.46 (s, 1H), 7.49 (d, 1H, J=3.0Hz), 7.23 (dd, 1H, J=3.0 Hz, 9.0 Hz), 7.17 (d, 1H, J=9.0 Hz), 5.25 (s,2H), 5.15 (s, 2H), 3.52 (s, 3H), 3.47 (s, 3H)

Step 2: Synthesis of Intermediate L2

A three-necked reactor equipped with a thermometer was charged with11.04 g (48.8 mmol) of the intermediate K2 synthesized in the step 1 and400 ml of ethanol under a nitrogen stream to prepare a solution. Afterthe addition of 6.40 g (58.56 mol) of 2-hydrazinopyridine to thesolution, the mixture was stirred at 25° C. for 3 hours. Aftercompletion of the reaction, 400 ml of distilled water was added to thereaction mixture to precipitate crystals. The crystals were filteredoff, washed with distilled water, and dried under vacuum to obtain 11.16g of an intermediate L2 as a light yellow solid (yield: 72%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 10.93 (s, 1H), 8.34 (s, 1H),8.07-8.12 (m, 1H), 7.61-7.67 (m, 1H), 7.52 (d, 1H, J=3.0 Hz), 7.23 (d,1H, J=8.5 Hz), 7.09 (d, 1H, J=9.0 Hz), 6.96 (dd, 1H, J=3.0 Hz, 9.0 Hz),6.73-6.78 (m, 1H), 5.20 (s, 2H), 5.18 (s, 2H), 3.42 (s, 3H), 3.40 (s,3H)

Step 3: Synthesis of Intermediate M2

A three-necked reactor equipped with a thermometer was charged with 10.0g (31.5 mmol) of the intermediate L2 synthesized in the step 2 and 300ml of THF under a nitrogen stream to prepare a solution. After theaddition of 14.0 g (34.7 mmol) of sodium hydride (50 to 72%, in oil) tothe solution over 30 minutes, the mixture was stirred at 25° C. for 30minutes. After the addition of 5.9 g (34.7 mmol) of2-chlorobenzothiazole, the reaction mixture was stirred for 8 hoursunder reflux with heating. 2000 ml of distilled water and 500 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 1000 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (THF:toluene=1:19) to obtain 8.8 g of an intermediate M2as a light yellow solid (yield: 62%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.69-8.75 (m, 1H), 8.19 (s, 1H),7.99 (dt, 1H, J=2.0 Hz, 7.5 Hz), 7.71-7.79 (m, 2H), 7.59-7.67 (m, 2H),7.37-7.43 (m, 1H), 7.28-7.33 (m, 1H), 7.15-7.21 (m, 2H), 7.01-7.04 (m,1H), 5.22 (s, 2H), 5.03 (s, 2H), 3.54 (s, 3H), 3.36 (s, 3H)

Step 4: Synthesis of Intermediate N2

A three-necked reactor equipped with a thermometer was charged with 8.4g (18.7 mmol) of the intermediate M2 synthesized in the step 3 and 300ml of ethanol under a nitrogen stream to prepare a solution. After theaddition of 17.7 g (93.2 mmol) of p-toluenesulfonic acid monohydrate,the mixture was stirred at 25° C. for 15 hours. 2000 ml of distilledwater and 500 ml of a saturated sodium chloride solution were added tothe reaction mixture, followed by extraction twice with 1500 ml of ethylacetate. The organic layer was dried over anhydrous sodium sulfate, andsodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and 150 ml of methanol was addedto the concentrate. Insoluble crystals were filtered off, washed withmethanol, and dried under vacuum to obtain 3.1 g of an intermediate N2as a yellow solid (yield: 46%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 9.28 (s, 1H), 9.01 (s, 1H),8.74-8.78 (m, 1H), 8.17 (dt, 1H, J=2.0 Hz, 7.5 Hz), 7.92 (dd, 1H, J=1.0Hz, 8.0 Hz), 7.86 (s, 1H), 7.72-7.76 (m, 1H), 7.58-7.63 (m, 1H), 7.51(d, 1H, J=8.0 Hz), 7.32 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.25-7.28 (m, 1H),7.21 (dt, 1H, J=1.0 Hz, 7.5 Hz), 6.70-6.72 (m, 2H)

Step 5: Synthesis of Compound 46

A three-necked reactor equipped with a thermometer was charged with 10.4g (24.8 mmol) of the intermediate A synthesized in the step 1 of Example1 (see “Synthesis of compound 1”) and 150 ml of THF under a nitrogenstream to prepare a solution. After the addition of 2.9 g (25.7 mmol) ofmethanesulfonyl chloride to the solution, the reactor was immersed in awater bath to adjust the temperature of the reaction mixture to 20° C.2.7 g (26.5 mmol) of triethylamine was added dropwise to the reactionmixture over 10 minutes. After the dropwise addition, the water bath wasremoved, and the mixture was stirred at 25° C. for 2 hours. After theaddition of 0.2 g (1.7 mmol) of 4-(dimethylamino)pyridine and 3.0 g (8.3mmol) of the intermediate N2 synthesized in the step 4 to the mixture,2.5 g (24.8 mmol) of triethylamine was added dropwise to the mixtureover 10 minutes. After the dropwise addition, the mixture was stirred at25° C. for 2 hours. After completion of the reaction, 2000 ml ofdistilled water and 500 ml of a saturated sodium chloride solution wereadded to the reaction mixture, followed by extraction twice with 1000 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (chloroform:THF=25:1) toobtain 1.8 g of a compound 46 as a light yellow solid (yield: 19%),

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.70-8.74 (m, 1H), 8.02 (dt, 1H,J=2.0 Hz, 7.5 Hz), 7.87 (s, 1H), 7.83 (d, 1H, J=2.5 Hz), 7.74-7.78 (m,1H), 7.62-7.67 (m, 2H), 7.42-7.46 (m, 1H), 7.34 (dt, 1H, J=1.0 Hz, 7.5Hz), 7.22 (dt, 1H, J=1.0 Hz, 7.5 Hz), 7.07-7.15 (m, 2H), 6.96-7.01 (m,4H), 6.90 (d, 2H, J=9.0 Hz), 6.88 (d, 2H, J=9.0 Hz), 6.41 (dd, 1H, J=1.5Hz, 17.5 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz,17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz,10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5 Hz), 4.18(t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz),2.56-2.71 (m, 2H), 2.25-2.50 (m, 6H), 2.12-2.21 (m, 2H), 1.93-2.01 (m,2H), 1.65-1.85 (m, 12H), 1.31-1.61 (m, 12H)

Example 85 Compound 47

Step 1: Synthesis of Intermediate 02

A three-necked reactor equipped with a thermometer was charged with 1.68g (10.61 mol) of o-tolylhydrazine and 50 ml of ethanol under a nitrogenstream to prepare a solution. After the addition of 1.34 g (13.26 mmol)of triethylamine to the solution, the mixture was stirred at 25° C. for10 minutes. After the addition of 2.00 g (8.84 mol) of the intermediateK2 synthesized in the step 1 of Example 84 (see “Synthesis of compound46”) to the mixture, the mixture was stirred at 25° C. for 1 hour. Aftercompletion of the reaction, 300 ml of distilled water and 50 ml of asaturated sodium chloride solution were added to the reaction mixture,followed by extraction twice with 100 ml of ethyl acetate. The organiclayer was dried over anhydrous sodium sulfate, and sodium sulfate wasseparated by filtration. The filtrate was concentrated using a rotaryevaporator, and the concentrate was purified by silica gel columnchromatography (THF:toluene=1:25) to obtain 2.81 g of an intermediate 02as a light yellow solid (yield: 96%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.16 (s, 1H), 7.69 (d, 1H, J=3.0Hz), 7.57 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.14-7.26 (m, 2H), 7.03-7.11 (m,2H), 6.95 (dd, 1H, J=3.0 Hz, 9.0 Hz), 6.81 (dt, 1H, J=1.0 Hz, 7.5 Hz),5.18 (s, 2H), 5.18 (s, 2H), 3.51 (s, 3H), 3.50 (s, 3H), 2.24 (s, 3H)

Step 2: Synthesis of Intermediate P2

A three-necked reactor equipped with a thermometer was charged with 2.78g (8.42 mol) of the intermediate 02 synthesized in the step 1 and 50 mlof THF under a nitrogen stream to prepare a solution. After the additionof 0.54 g (13.46 mmol) of sodium hydride (50 to 72%, in oil) to thesolution at 25° C. over 15 minutes, the mixture was stirred for 30minutes. After the addition of 2.14 g (12.62 mmol) of2-chlorobenzothiazole, the reaction mixture was stirred for 2 hoursunder reflux with heating. After completion of the reaction, 400 ml ofdistilled water and 50 ml of a saturated sodium chloride solution wereadded to the reaction mixture, followed by extraction twice with 150 mlof ethyl acetate. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (THF:toluene=3:100) toobtain 2.66 g of an intermediate P2 as a light yellow solid (yield:68%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.76 (d, 1H, J=3.0 Hz), 7.72 (dd,1H, J=1.0 Hz, 8.0 Hz), 7.60 (dd, 1H, J=1.0 Hz, 8.0 Hz), 7.54 (s, 1H),7.41-7.48 (m, 3H), 7.25-7.34 (m, 2H), 7.11-7.21 (m, 1H), 6.95-7.03 (m,2H), 5.22 (s, 2H), 4.98 (s, 2H), 3.55 (s, 3H), 3.26 (s, 3H), 2.16 (s,31H)

Step 3: Synthesis of Intermediate Q2

A three-necked reactor equipped with a thermometer was charged with 2.65g (5.72 mmol) of the intermediate P2 synthesized in the step 2 and 80 mlof ethanol under a nitrogen stream to prepare a solution. After theaddition of 5.44 mg (28.58 mmol) of p-toluenesulfonic acid monohydrateto the solution, the mixture was stirred for 15 hours. After completionof the reaction, the reaction mixture was concentrated using a rotaryevaporator, and 40 ml of methanol was added to the concentrate.Insoluble crystals were filtered off, washed with methanol, and driedunder vacuum to obtain 1.88 g of an intermediate Q2 as a yellow solid(yield: 88%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, DMSO-d₆, TMS, δ ppm): 7.90 (dd, 1H, J=1.0 Hz, 8.0 Hz),7.46-7.58 (m, 5H), 7.39-7.42 (m, 1H), 7.25-7.33 (m, 2H), 7.18 (dt, 1H,J=1.0 Hz, 7.5 Hz), 7.10-7.15 (m, 2H), 6.69 (s, 1H), 6.69 (s, 1H), 2.29(s, 3H)

Step 4: Synthesis of Compound 47

A three-necked reactor equipped with a thermometer was charged with 5.36g (12.78 mmol) of the intermediate A synthesized in the step 1 ofExample 1 (see “Synthesis of compound 1”) and 60 ml of THF under anitrogen stream to prepare a solution. After the addition of 1.52 g(13.22 mmol) of methanesulfonyl chloride to the solution, the reactorwas immersed in a water bath to adjust the temperature of the reactionmixture to 20° C. 1.38 g (13.7 mmol) of triethylamine was added dropwiseto the reaction mixture over 5 minutes. After removing the water bath,the mixture was stirred at 25° C. for 2 hours. After the addition of 0.1g (0.82 mmol) of 4-(dimethylamino)pyridine and 1.60 g (4.26 mmol) of theintermediate Q2 synthesized in the step 3 to the mixture, 1.30 g (12.78mmol) of triethylamine was added dropwise to the mixture over 5 minutes.After the dropwise addition, the mixture was stirred at 25° C. for 2hours. After completion of the reaction, 400 ml of distilled water and100 ml of a saturated sodium chloride solution were added to thereaction mixture, followed by extraction twice with 200 ml ofchloroform. The organic layer was dried over anhydrous sodium sulfate,and sodium sulfate was separated by filtration. The filtrate wasconcentrated using a rotary evaporator, and the concentrate was purifiedby silica gel column chromatography (chloroform:THF=40:1) to obtain 1.04g of a compound 47 as a light yellow solid (yield: 21%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.84 (d, 1H, J=3.0 Hz), 7.73 (dt,1H, J=1.0 Hz, 8.0 Hz), 7.61 (d, 1H, J=8.0 Hz), 7.44-7.52 (m, 3H),7.27-7.34 (m, 2H), 7.15-7.20 (m, 2H), 7.10 (dd, 1H, J=3.0 Hz, 9.0 Hz),7.05 (d, 1H, J=9.0 Hz), 7.01 (d, 2H, J=9.0 Hz), 6.99 (d, 2H, J=9.0 Hz),6.90 (d, 2H, J=9.0 Hz), 6.89 (d, 2H, J=9.0 Hz), 6.41 (dd, 1H, J=1.5 Hz,17.5 Hz), 6.41 (dd, 1H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz,17.5 Hz), 6.13 (dd, 1H, J=10.5 Hz, 17.5 Hz), 5.82 (dd, 1H, J=1.5 Hz,10.5 Hz), 5.82 (dd, 1H, J=1.5 Hz, 10.5 Hz), 4.18 (t, 2H, J=6.5 Hz), 4.18(t, 2H, J=6.5 Hz), 3.96 (t, 2H, J=6.5 Hz), 3.95 (t, 2H, J=6.5 Hz),2.56-2.72 (m, 2H), 2.42-2.51 (m, 1H), 2.28-2.40 (m, 5H), 2.14-2.22 (m,2H), 2.14 (s, 3H), 1.65-1.91 (m, 14H), 1.41-1.57 (m, 10H), 1.19-1.31 (m,2H)

Phase Transition Temperature Measurement 3

10 mg of the compound (compounds 34 to 47) was weighed, and placed in asolid state between two glass substrates provided with a polyimidealignment film subjected to a rubbing treatment. The substrates wereplaced on a hot plate, heated from 40° C. to 250° C., and cooled to 40°C. A change in structure when the temperature was changed was observedusing a polarizing microscope.

The phase transition temperature measurement results are shown in Table5.

TABLE 5 Compound No. Phase transition temperature Example 72 Compound 34

Example 73 Compound 35

Example 74 Compound 36

Example 75 Compound 37

Example 76 Compound 38

Example 77 Compound 39

Example 78 Compound 40

Example 79 Compound 41

Example 80 Compound 42

Example 81 Compound 43

Example 82 Compound 44

Example 83 Compound 45

Example 84 Compound 46

Example 85 Compound 47

Examples 86 to 88

1.0 g of each of the compounds 34 to 36 respectively obtained inExamples 72 to 74, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 39 to 41).

Example 89

1.0 g of the compound 37 obtained in Example 75, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 3.0 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 42.

Examples 90 to 93

1.0 g of each of the compounds 38 to 41 respectively obtained inExamples 76 to 79, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 43 to 46).

Example 94

1.0 g of the compound 42 obtained in Example 80, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 3.0 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 47.

Examples 95 to 97

1.0 g of each of the compounds 43 to 45 respectively obtained inExamples 81 to 83, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 48 to 50).

Example 98

1.0 g of the compound 46 obtained in Example 84, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of chloroform. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 51.

Example 99

1.0 g of the compound 47 obtained in Example 85, 30 mg of thephotoinitiator A, and 100 mg of a 1% cyclopentanone solution of thesurfactant A were dissolved in 2.3 g of cyclopentanone. The solution wasfiltered through a disposable filter having a pore size of 0.45 μm toobtain a polymerizable composition 52.

Retardation Measurement and Wavelength Dispersion Evaluation III (i)Formation of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 39 to 52 was applied to atransparent glass substrate provided with a polyimide alignment filmsubjected to a rubbing treatment using a #4 wire bar. The resulting filmwas dried for 1 minute at the temperature shown in Table 6, andsubjected to an alignment treatment for 1 minute at the temperatureshown in Table 6 to form a liquid crystal layer. UV rays were applied tothe liquid crystal layer at a dose of 2000 mJ/cm² at the temperatureshown in Table 6 to effect polymerization to prepare a wavelengthdispersion measurement sample.

(ii) Retardation Measurement and Wavelength Dispersion Evaluation

The retardation was measured, and the wavelength dispersion wasevaluated in the same manner as described above using the resultingsamples.

Table 6 shows the thickness (μm) of the liquid crystal polymer filmsobtained by polymerizing the polymerizable compositions, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

TABLE 6 Polymerizable Alignment compound Drying treatment Exposure RePolymerizable Ratio temperature temperature temperature Thickness (548.5composition Type (%) (° C.) (° C.) (° C.) (μm) nm) α β Example 86 39Compound 34 100 150 150 145 2.189 170.668 0.868 1.025 Example 87 40Compound 35 100 140 140 100 1.610 119.785 0.810 1.036 Example 88 41Compound 36 100 150 23 23 1.493 131.210 0.893 1.002 Example 89 42Compound 37 100 120 23 23 1.810 145.979 0.863 1.018 Example 90 43Compound 38 100 130 23 23 1.525 111.539 0.885 1.048 Example 91 44Compound 39 100 130 23 23 1.660 118.003 0.817 1.011 Example 92 45Compound 40 100 140 23 23 1.763 136.324 0.891 1.022 Example 93 46Compound 41 100 150 23 23 1.304 91.456 0.903 1.010 Example 94 47Compound 42 100 170 110 105 1.237 132.494 0.910 1.019 Example 95 48Compound 43 100 130 23 23 1.501 136.780 0.917 0.999 Example 96 49Compound 44 100 165 23 23 1.498 127.091 0.887 1.012 Example 97 50Compound 45 100 130 65 65 1.511 129.743 0.903 1.011 Example 98 51Compound 46 100 120 70 70 1.984 197.529 0.957 1.000 Example 99 52Compound 47 100 150 120 115 1.531 107.094 0.899 1.020

As is clear from the results shown in Table 6, it was confirmed that thepolymers obtained in Examples 86 to 99 using the compounds 34 to 47according to the invention were an optically anisotropic article. Theoptically anisotropic articles showed ideal wideband wavelengthdispersion in which the value α was smaller than 1, and the value β waslarger than 1, or almost equal to 1.

Example 100 Synthesis of Compound 48

Step 1: Synthesis of Intermediate R2

A four-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mmol) of cesium carbonate and 1.93 g (14.5 mmol) of1-bromo-2-butyne to the solution, the mixture was stirred at 25° C. for204 hours, After completion of the reaction, the reaction mixture wasadded to 200 ml of water, and extracted with 300 ml of ethyl acetate.After drying the ethyl acetate layer over anhydrous sodium sulfate,sodium sulfate was separated by filtration. Ethyl acetate was evaporatedfrom the filtrate under reduced pressure using a rotary evaporator toobtain a brown solid. The brown solid was purified by silica gel columnchromatography (n-hexane:ethyl acetate=85:15) to obtain 1.25 g of anintermediate R2 as a white solid (yield: 47.5%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 M Hz, CDCl₃, TMS, δ ppm): 7.63 (dd, 1H, J=1.3 Hz, 7.8 Hz),7.58 (dd, 1H, J=1.3 Hz, 7.8 Hz), 7.29 (ddd, 1H, J=1.3 Hz, 7.8 Hz, 7.8Hz), 7.10 (ddd, 1H, J=1.3 Hz, 7.8 Hz, 7.8 Hz), 4.56 (q, 2H, J=2.5 Hz),4.36 (s, 2H), 1.84 (t, 3H, J=2.5 Hz)

Step 2: Synthesis of Compound 48

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 387 mg (1.78 mmol) of theintermediate R2 synthesized in the step 1, 41.4 mg (0.165 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.54 g of a compound 48 as a light yellow solid (yield:84.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.90 (s, 1H), 7.78 (d, 1H, J=1.3Hz), 7.67-7.73 (m, 2H), 7.35 (ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5 Hz), 7.18(ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5 Hz), 7.09-7.15 (m, 2H), 6.95-7.01 (m,4H), 6.85-6.91 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.0 Hz), 6.13 (dd, 2H,J=10.5 Hz, 17.0 Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 5.06 (d, 2H,J=2.0 Hz), 4.18 (t, 4H, J=6.0 Hz), 3.95 (t, 4H, J=6.0 Hz), 2.55-2.76 (m,4H), 2.26-2.43 (m, 8H), 1.64-1.83 (m, 19H), 1.41-1.55 (m, 8H)

Example 101 Synthesis of Compound 49

Step 1: Synthesis of Intermediate S2

A three-necked reactor equipped with a thermometer was charged with 2.00g (12.1 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 7.88 g(24.2 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. 2.50 g (14.5 mmol) of 10-chloro-3-decyne was added dropwise tothe mixture over 5 minutes. After the dropwise addition, the mixture wasstirred at 25° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 200 ml of water, and extracted with 300 mlof ethyl acetate. After drying the ethyl acetate layer over anhydroussodium sulfate, sodium sulfate was separated by filtration. Ethylacetate was evaporated from the filtrate under reduced pressure using arotary evaporator to obtain a brown solid. The brown solid was purifiedby silica gel column chromatography (n-hexane:ethyl acetate=85:15) toobtain 1.51 g of an intermediate S2 as a white solid (yield: 41.4%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.5 Hz, 7.5 Hz),7.53 (dd, 1H, J=1.5 Hz, 7.5 Hz), 7.28 (ddd, 1H, J=1.5 Hz, 7.5 Hz, 7.5Hz), 7.06 (ddd, 1H, J=1.5 Hz, 7.5 Hz, 7.5 Hz), 4.23 (s, 2H), 3.75 (t,2H, J=7.5 Hz), 2.09-2.21 (m, 4H), 1.75 (tt, 2H, J=7.5 Hz, 7.5 Hz),1.35-1.54 (m, 6H), 1.11 (t, 3H, J=7.5 Hz)

Step 2: Synthesis of Compound 49

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 534 mg (1.78 mmol) of theintermediate S2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 3 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=92:8) to obtain 1.62 g of a compound 49 as a light yellow solid(yield: 83.8%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.75 (d, 1H, J=1.5 Hz), 7.65-7.71(m, 3H), 7.34 (ddd, 1H, J=1.5 Hz, 7.8 Hz, 7.8 Hz), 7.17 (ddd, 1H, J=1.5Hz, 7.8 Hz, 7.8 Hz), 7.08-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.91 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.5Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.31 (t, 2H, J=7.5 Hz), 4.18 (t,4H, J=6.5 Hz), 3.94 (t, 4H, J=6.5 Hz), 2.54-2.74 (m, 4H), 2.25-2.40 (m,8H), 2.09-2.19 (m, 4H), 1.63-1.85 (m, 18H), 1.38-1.55 (m, 14H), 1.09 (t,3H, J=7.5 Hz)

Example 102 Synthesis of Compound 50

Step 1: Synthesis of Intermediate T2

A three-necked reactor equipped with a thermometer was charged with 3.00g (18.2 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 11.9 g(36.4 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. 41.5 g (21.8 mmol) of chloromethylphenylsulfone was addeddropwise to the mixture over 5 minutes. After the dropwise addition, themixture was stirred at 25° C. for 6 hours. After completion of thereaction, 300 ml of water was added to the reaction mixture, followed byextraction twice with 200 ml of ethyl acetate. The organic layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator, andthe concentrate was purified by silica gel column chromatography(n-hexane:ethyl acetate=75:25) to obtain 1.81 g of an intermediate T2 asa white solid (yield: 31.2%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.85-7.90 (m, 2H), 7.55 (dd, 1H,J=1.5 Hz, 7.3 Hz), 7.32-7.43 (m, 3H), 7.13-7.21 (m, 2H), 7.05 (ddd, 1H,J=1.5 Hz, 7.3 Hz, 7.3 Hz), 5.25 (s, 2H), 4.99 (s, 2H)

Step 2: Synthesis of Compound 50

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 567 mg (1.78 mmol) of theintermediate T2 synthesized in the step 1, 41.4 mg (0,178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethyl acetate=9:1)to obtain 1.53 g of a compound 50 as a light yellow solid (yield:77.3%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.50 (s, 1H), 7.87-7.95 (m, 2H),7.72 (d, 1H, J=1.3 Hz), 7.61 (d, 1H, J=7.5 Hz), 7.33-7.45 (m, 4H), 7.27(ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5 Hz), 7.16-7.20 (m, 2H), 7.15 (ddd, 1H,J=1.3 Hz, 7.5 Hz, 7.5 Hz), 6.94-7.01 (m, 4H), 6.84-6.91 (m, 4H), 6.40(dd, 2H, J=1.5 Hz, 17.5 Hz), 6.12 (dd, 2H, J=10.0 Hz, 17.5 Hz), 5.82(dd, 2H, J=1.5 Hz, 10.0 Hz), 5.61 (s, 2H), 4.17 (t, 4H, J=6.5 Hz), 3.94(t, 4H, J=6.5 Hz), 2.73-2.86 (m, 1H), 2.54-2.71 (m, 3H), 2.40-2.49 (m,2H), 2.29-2.39 (m, 6H), 1.62-1.84 (m, 16H), 1.40-1.54 (m, 8H)

Example 103 Synthesis of Compound 51

Step 1: Synthesis of Intermediate U2

A three-necked reactor equipped with a thermometer was charged with 3.00g (18.2 mmol) of 2-hydrazinobenzothiazole and 40 ml of DMF under anitrogen stream to prepare a solution. After the addition of 11.9 g(36.4 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. 4.34 g (21.8 mmol) of phenacyl bromide was added dropwise tothe mixture over 5 minutes. After the dropwise addition, the mixture wasstirred at 25° C. for 5 hours. After completion of the reaction, 250 mlof water was added to the reaction mixture, followed by extraction twicewith 100 ml of ethyl acetate. The organic layer was dried over anhydroussodium sulfate, and sodium sulfate was separated by filtration. Thefiltrate was concentrated using a rotary evaporator, and the concentratewas purified by silica gel column chromatography (n-hexane:ethylacetate=75:25) to obtain 1.79 g of an intermediate U2 as a white solid(yield: 34.7%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.99 (dd, 2H, J=1.3 Hz, 7.5 Hz),7.59-7.66 (m, 2H), 7.44-7.53 (m, 3H), 7.25 (ddd, 1H, J=1.3 Hz, 7.5 Hz,7.5 Hz), 7.08 (ddd, 1H, J=1.3 Hz, 7.5 Hz, 7.5 Hz), 5.31 (s, 2H), 4.65(s, 2H)

Step 2: Synthesis of Compound 51

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 504 mg (1.78 mmol) of theintermediate U2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=85:15) to obtain 1.59 g of a compound 51 as a light yellow solid(yield: 82.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 8.12 (dd, 2H, J=1.0 Hz, 7.5 Hz),7.76 (d, 1H, J=2.5 Hz), 7.72 (dd, 1H, J=1.0 Hz, 7.5 Hz), 7.60-7.69 (m,2H), 7.53-7.59 (m, 2H), 7.42 (s, 1H), 7.34 (ddd, 1H, J=1.0 Hz, 7.5 Hz,7.5 Hz), 7.19 (ddd, 1H, J=1.0 Hz, 7.5 Hz, 7.5 Hz), 7.06-7.12 (m, 2H),6.95-7.01 (m, 4H), 6.86-6.93 (m, 4H), 6.40 (dd, 2H, J=1.5 Hz, 17.5 Hz),6.13 (dd, 2H, J=10.5 Hz, 17.5 Hz), 5.83 (dd, 2H, J=1.5 Hz, 10.5 Hz),5.82 (s, 2H), 4.18 (t, 4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 2.55-2.72(m, 2H), 2.20-2.42 (m, 6H), 1.87-2.09 (m, 4H), 1.64-1.85 (m, 12H),1.32-1.56 (m, 12H)

Example 104 Synthesis of Compound 52

Step 1: Synthesis of Intermediate V2

A three-necked reactor equipped with a thermometer was charged with 3.00g (18.2 mmol) of 2-hydrazinobenzothiazole and 30 ml of DMF under anitrogen stream to prepare a solution. After the addition of 11.9 g(36.4 mol) of cesium carbonate to the solution, the mixture was cooledto 0° C. 4.03 g (21.8 mmol) of 2-phenylethyl bromide was added dropwiseto the mixture over 5 minutes. After the dropwise addition, the mixturewas stirred at 25° C. for 25 hours. After completion of the reaction,250 ml of water was added to the reaction mixture, followed byextraction twice with 100 ml of ethyl acetate. The organic layer wasdried over anhydrous sodium sulfate, and sodium sulfate was separated byfiltration. The filtrate was concentrated using a rotary evaporator, andthe concentrate was purified by silica gel column chromatography(n-hexane:ethyl acetate=78:22) to obtain 2.10 g of an intermediate V2 asa white solid (yield: 42.9%).

The structure of the target product was identified by ¹H-NMR.

¹H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.60 (dd, 1H, J=1.3 Hz, 7.8 Hz),7.56 (dd, 1H, J=1.3 Hz, 7.8 Hz), 7.20-7.36 (m, 6H), 7.07 (ddd, 1H, J=1.3Hz, 7.8 Hz, 7.8 Hz), 4.05 (s, 2H), 4.01 (t, 2H, J=7.3 Hz), 3.07 (t, 2H,J=7.3 Hz)

Step 2: Synthesis of Compound 52

A three-necked reactor equipped with a thermometer was charged with 1.50g (1.60 mmol) of the intermediate B synthesized in the step 2 of Example1 (see “Synthesis of compound 1”), 477 mg (1.78 mmol) of theintermediate V2 synthesized in the step 1, 41.4 mg (0.178 mmol) of(±)-10-camphorsulfonic acid, 16 ml of THF, and 4 ml of ethanol under anitrogen stream to prepare a homogeneous solution. The solution wasstirred at 40° C. for 5 hours. After completion of the reaction, thereaction mixture was added to 100 ml of water, and extracted with 200 mlof chloroform. The organic layer was dried over anhydrous sodiumsulfate, and sodium sulfate was separated by filtration. The filtratewas concentrated using a rotary evaporator, and the concentrate waspurified by silica gel column chromatography (toluene:ethylacetate=92:8) to obtain 1.56 g of a compound 52 as a light yellow solid(yield: 82.3%).

The structure of the target product was identified by ¹H-NMR.

1H-NMR (500 MHz, CDCl₃, TMS, δ ppm): 7.76 (d, 1H, J=1.5 Hz), 7.68-7.73(m, 3H), 7.29-7.39 (m, 5H), 7.22-7.26 (m, 1H), 7.19 (ddd, 1H, J=1.5 Hz,8.5 Hz, 8.5 Hz), 7.08-7.14 (m, 2H), 6.95-7.02 (m, 4H), 6.86-6.92 (m,4H), 6.40 (dd, 2H, J=1.5 Hz, 17.0 Hz), 6.13 (dd, 2H, J=10.5 Hz, 17.0Hz), 5.82 (dd, 2H, J=1.5 Hz, 10.5 Hz), 4.54 (t, 2H, J=5.5 Hz), 4.18 (t,4H, J=6.5 Hz), 3.95 (t, 4H, J=6.5 Hz), 3.06 (t, 2H, J=5.5 Hz), 2.56-2.71(m, 3H), 2.42-2.53 (m, 1H), 2.13-2.40 (m, 8H), 1.59-1.84 (m, 16H),1.41-1.56 (m, 8H)

Phase Transition Temperature Measurement 4

10 mg of the compound (compounds 48 to 52) was weighed, and placed in asolid state between two glass substrates provided with a polyimidealignment film subjected to a rubbing treatment. The substrates wereplaced on a hot plate, heated from 40° C. to 250° C., and cooled to 40°C. A change in structure when the temperature was changed was observedusing a polarizing microscope.

The phase transition temperature measurement results are shown in Table7.

TABLE 7 Compound No. Phase transition temperature Example 100 Compound48

Example 101 Compound 49

Example 102 Compound 50

Example 103 Compound 51

Example 104 Compound 52

Examples 105 to 109

1.0 g of each of the compounds 48 to 52 respectively obtained inExamples 100 to 104, 30 mg of the photoinitiator A, and 100 mg of a 1%cyclopentanone solution of the surfactant A were dissolved in 2.3 g ofcyclopentanone. The solution was filtered through a disposable filterhaving a pore size of 0.45 μm to obtain a polymerizable composition(polymerizable compositions 53 to 57).

Retardation Measurement and Wavelength Dispersion Evaluation IV (i)Formation of Liquid Crystal Layer Using Polymerizable Composition

Each of the polymerizable compositions 53 to 57 was applied to atransparent glass substrate provided with a polyimide alignment filmsubjected to a rubbing treatment using a #4 wire bar. The resulting filmwas dried for 1 minute at the temperature shown in Table 8, andsubjected to an alignment treatment for 1 minute at the temperatureshown in Table 8 to form a liquid crystal layer. UV rays were applied tothe liquid crystal layer at a dose of 2000 mJ/cm² at the temperatureshown in Table 8 to effect polymerization to prepare a wavelengthdispersion measurement sample.

(ii) Retardation Measurement and Wavelength Dispersion Evaluation

The retardation was measured, and the wavelength dispersion wasevaluated in the same manner as described above using the resultingsamples.

Table 8 shows the thickness (km) of the liquid crystal polymer filmsobtained by polymerizing the polymerizable compositions, the retardation(Re) at a wavelength of 548.5 nm, and the values α and β.

TABLE 8 Polymerizable Alignment compound Drying treatment Exposure RePolymerizable Ratio temperature temperature temperature Thickness (548.5composition Type (%) (° C.) (° C.) (° C.) (μm) nm) α β Example 105 53Compound 48 100 130 23 23 1.466 123.35 0.898 1.037 Example 106 54Compound 49 100 130 23 23 1.671 120.22 0.830 1.042 Example 107 55Compound 50 100 155 100 90 1.406 112.79 0.932 1.002 Example 108 56Compound 51 100 155 120 120 1.774 104.85 0.886 1.016 Example 109 57Compound 52 100 110 23 23 1.435 126.26 0.854 1.012

As is clear from the results shown in Table 8, it was confirmed that thepolymers obtained in Examples 105 to 109 using the compounds 48 to 52according to the invention were an optically anisotropic article. Theoptically anisotropic articles showed ideal wideband wavelengthdispersion in which the value α was smaller than 1, and the value β waslarger than 1.

Example 110

19.3 parts of the compound 4 obtained in Example 4, 0.6 parts of aphotoinitiator B (“Irgacure 379” manufactured by BASF Japan Ltd.), and5.8 parts of a 1% cyclopentanone solution of a surfactant B (“SurflonS-420” manufactured by AGC Seimi Chemical Co., Ltd.) were dissolved in74.2 parts of cyclopentanone. The solution was filtered through adisposable filter having a pore size of 0.6 μm to obtain a polymerizablecomposition 58.

Example 111

A polymerizable composition 59 was obtained in the same manner as inExample 110, except that the compound 13 obtained in Example 26 was usedinstead of the compound 4 obtained in Example 4.

Example 112

A polymerizable composition 60 was obtained in the same manner as inExample 110, except that the compound 22 obtained in Example 35 was usedinstead of the compound 4 obtained in Example 4.

Comparative Example 3

A polymerizable composition 61 was obtained in the same manner as inExample 110, except that the compound A obtained in Synthesis Example 1was used instead of the compound 4 obtained in Example 4.

Retardation Measurement and Reflected Luminance Evaluation

The polymerizable compositions 58 to 61 were polymerized by thefollowing method to obtain polymers. The retardation was measured, andthe reflected luminance was evaluated using the resulting polymers.

Production of Retardation Film

One side of a support (“Zeonor Film ZF16” manufactured by ZeonCorporation) was subjected to an alignment treatment by rubbing. Each ofthe polymerizable compositions 58 to 61 was applied to the side of thesupport subjected to the alignment treatment using a spin coater so thatthe thickness after drying was 2.5 μm, 1.9 μm, 1.9 μm, or 1.4 μm,respectively. The polymerizable composition layer was dried by heatingthe polymerizable composition layer at 130° C. for 2 minutes using anoven. Note that the polymerizable composition 60 was heated at 105° C. Alaminate consisting of the support and the dried polymerizablecomposition layer formed on the support was thus obtained.

UV rays were applied to the laminate using a metal halide lamp topolymerize the polymerizable composition. UV rays were applied at anilluminance of 16 mW/cm² and a dose of 100 mJ/cm². A retardation filmconsisting of the support and an optically anisotropic article layerprovided on the support was thus obtained. The thickness of theresulting optically anisotropic article layer was 2.5 μm, 1.9 μm, 1.9μm, or 1.4 μm, respectively.

The retardation Re (550) of the retardation film at a wavelength 2 of550 nm was measured using a retardation analyzer (“AxoScan” manufacturedby AXOMETRICS), The results are shown in Table 9.

Production of Circular Polarizer

The retardation film and a linear polarizer (“HLC2-5618” manufactured bySANRITZ Corporation) were bonded using an optical transparent adhesive(“LUCIACS” manufactured by Nitto Denko Corporation) to produce acircular polarizer. The relative angle formed by the absorption axisdirection of the linear polarizer and the slow axis direction (directionparallel to the rubbing direction) of the retardation film was set to450

Calculation of Reflected Luminance of Circular Polarizer

An aluminum-deposited PET film (“Metalumy TS #50” manufactured by TorayAdvanced Film Co., Ltd.) was bonded to the retardation film of thecircular polarizer using the optical transparent adhesive to obtain ameasurement sample. The reflection spectrum of the sample (50reflection) was measured using a spectrophotometer (“V7200” manufacturedby JASCO Corporation). The measurement wavelength was 380 to 780 nm.

The resulting reflection spectrum was multiplied by a color-matchingfunction y(λ), and the resulting values were integrated to calculate thereflected luminance Y. A reference white light source was a D65 lightsource. The results are shown in Table 9.

TABLE 9 Polymerizable compound Reflected Polymerizable Ratio ThicknessRetardation luminance Y composition Type (%) (μm) (550 nm) (%) Example110 58 Compound 4  100 2.5 141 1.44 Example 111 59 Compound 13 100 1.9141 1.55 Example 112 60 Compound 22 100 1.9 139 1.65 Comparative 61Compound A  100 1.4 140 1.70 Example 3

As is clear from the results shown in Table 9, it was confirmed that thecircular polarizers obtained in Examples 110 to 112 showed a reflectedluminance lower than that of the circular polarizer obtained inComparative Example 3 (i.e., the circular polarizers obtained inExamples 110 to 112 exhibited excellent performance).

1-18. (canceled)
 19. A polymer obtained by polymerizing a polymerizablecompound represented by a formula (I),

or a polymerizable composition comprising at least one polymerizablecompound represented by a formula (I) and an initiator; wherein Y¹ to Y⁸are independently a chemical single bond, —O—, —S—, —O—C(═O)—,—C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—, —O—C(═O)—NR¹—,—NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹ is a hydrogenatom or an alkyl group having 1 to 6 carbon atoms, G¹ and G² areindependently a substituted or unsubstituted divalent linear aliphaticgroup having 1 to 20 carbon atoms that optionally includes —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or—C(═O)—, provided that a case where the aliphatic group includes two ormore contiguous —O— or —S— is excluded, R² is a hydrogen atom or analkyl group having 1 to 6 carbon atoms, Z¹ and Z² are independently analkenyl group having 2 to 10 carbon atoms that is unsubstituted, orsubstituted with a halogen atom, A^(x) is an organic group having 2 to30 carbon atoms that includes at least one aromatic ring selected from agroup consisting of an aromatic hydrocarbon ring and a heteroaromaticring, A^(y) is a hydrogen atom, a substituted or unsubstituted alkylgroup having 1 to 20 carbon atoms, a substituted or unsubstitutedalkenyl group having 2 to 20 carbon atoms, a substituted orunsubstituted alkynyl group having 1 to 20 carbon atoms, a substitutedor unsubstituted cycloalkyl group having 3 to 12 carbon atoms,—C(═O)—R³, —SO₂—R⁴, —C(═S)NH—R⁹, or an organic group having 2 to 30carbon atoms that includes at least one aromatic ring selected from agroup consisting of an aromatic hydrocarbon ring and a heteroaromaticring, R³ is a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted alkenyl group having 2 to20 carbon atoms, a substituted or unsubstituted cycloalkyl group having3 to 12 carbon atoms, or an aromatic hydrocarbon group having 5 to 12carbon atoms, R⁴ is an alkyl group having 1 to 20 carbon atoms, analkenyl group having 2 to 20 carbon atoms, a phenyl group, or a4-methylphenyl group, R⁹ is a substituted or unsubstituted alkyl grouphaving 1 to 20 carbon atoms, a substituted or unsubstituted alkenylgroup having 2 to 20 carbon atoms, a substituted or unsubstitutedcycloalkyl group having 3 to 12 carbon atoms, or a substituted orunsubstituted aromatic group having 5 to 20 carbon atoms, provided thatthe aromatic ring included in A^(x) and A^(y) is substituted orunsubstituted, and A^(x) and A^(y) are optionally bonded to each otherto form a ring, A¹ is a substituted or unsubstituted trivalent aromaticgroup, A² and A³ are independently a substituted or unsubstituteddivalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, A⁴ andA⁵ are independently a substituted or unsubstituted divalent aromaticgroup having 6 to 30 carbon atoms, and Q¹ is a hydrogen atom, or asubstituted or unsubstituted alkyl group having 1 to 6 carbon atoms. 20.The polymer according to claim 19, the polymer being a liquidcrystalline polymer.
 21. An optically anisotropic article comprising thepolymer according to claim
 20. 22. A carbonyl compound represented by aformula (4),

wherein Y¹ to Y⁸ are independently a chemical single bond, —O—, —S—,—O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—,—O—C(═O)—NR¹—, —NR¹—C(═O)—O—, —NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, G¹ andG² are independently a substituted or unsubstituted divalent linearaliphatic group having 1 to 20 carbon atoms that optionally includes—O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—,—NR²—, or —C(═O)—, provided that a case where the aliphatic groupincludes two or more contiguous —O— or —S— is excluded, R² is a hydrogenatom or an alkyl group having 1 to 6 carbon atoms, Z¹ and Z² areindependently an alkenyl group having 2 to 10 carbon atoms that isunsubstituted, or substituted with a halogen atom, A¹ is a substitutedor unsubstituted trivalent aromatic group, A² and A³ are independently asubstituted or unsubstituted divalent alicyclic hydrocarbon group having3 to 30 carbon atoms, A⁴ and A⁵ are independently a substituted orunsubstituted divalent aromatic group having 6 to 30 carbon atoms, andQ¹ is a hydrogen atom, or a substituted or unsubstituted alkyl grouphaving 1 to 6 carbon atoms.
 23. The carbonyl compound according to claim22, wherein A¹ is a substituted or unsubstituted trivalent benzene ringgroup, or a substituted or unsubstituted trivalent naphthalene ringgroup.
 24. The carbonyl compound according to claim 22, wherein A² andA³ are independently a substituted or unsubstituted divalent cyclohexylgroup.
 25. The carbonyl compound according to claim 22, wherein Z¹ andZ² are independently CH₂═CH—, CH₂═C(CH₃)—, or CH₂═C(Cl)—.
 26. A methodfor producing a polymerizable compound represented by a formula (I), themethod comprising reacting the carbonyl compound according to claim 22with a hydrazine compound represented by the following formula,

wherein A^(x) is an organic group having 2 to 30 carbon atoms thatincludes at least one aromatic ring selected from a group consisting ofan aromatic hydrocarbon ring and a heteroaromatic ring, A^(y) is ahydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted alkenyl group having 2 to20 carbon atoms, a substituted or unsubstituted alkynyl group having 1to 20 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 12 carbon atoms, —C(═O)—R³, —SO₂—R⁴, —C(═S)NH—R⁹, or anorganic group having 2 to 30 carbon atoms that includes at least onearomatic ring selected from a group consisting of an aromatichydrocarbon ring and a heteroaromatic ring, R³ is a substituted orunsubstituted alkyl group having 1 to 20 carbon atoms, a substituted orunsubstituted alkenyl group having 2 to 20 carbon atoms, a substitutedor unsubstituted cycloalkyl group having 3 to 12 carbon atoms, or anaromatic hydrocarbon group having 5 to 12 carbon atoms, R⁴ is an alkylgroup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a phenyl group, or a 4-methylphenyl group, R⁹ is asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms,a substituted or unsubstituted cycloalkyl group having 3 to 12 carbonatoms, or a substituted or unsubstituted aromatic group having 5 to 20carbon atoms, provided that the aromatic ring included in A^(x) andA^(y) is substituted or unsubstituted, and A^(x) and A^(y) areoptionally bonded to each other to form a ring,

wherein A^(x) and A^(y) are the same as defined above, Y¹ to Y⁸ areindependently a chemical single bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—,—NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹ is a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, G¹ and G² are independently asubstituted or unsubstituted divalent linear aliphatic group having 1 to20 carbon atoms that optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)—, provided thata case where the aliphatic group includes two or more contiguous —O— or—S— is excluded, R² is a hydrogen atom or an alkyl group having 1 to 6carbon atoms, Z¹ and Z² are independently an alkenyl group having 2 to10 carbon atoms that is unsubstituted, or substituted with a halogenatom, A¹ is a substituted or unsubstituted trivalent aromatic group, A²and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms, A⁴ and A⁵ areindependently a substituted or unsubstituted divalent aromatic grouphaving 6 to 30 carbon atoms, and Q¹ is a hydrogen atom, or a substitutedor unsubstituted alkyl group having 1 to 6 carbon atoms.
 27. A methodcomprising: reacting a raw material comprising the carbonyl compoundaccording to claim 22 to producing a polymerizable compound representedby a formula (I),

wherein A^(x) is an organic group having 2 to 30 carbon atoms thatincludes at least one aromatic ring selected from a group consisting ofan aromatic hydrocarbon ring and a heteroaromatic ring, A^(y) is ahydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20carbon atoms, a substituted or unsubstituted alkenyl group having 2 to20 carbon atoms, a substituted or unsubstituted alkynyl group having 1to 20 carbon atoms, a substituted or unsubstituted cycloalkyl grouphaving 3 to 12 carbon atoms, —C(═O)—R³, —SO₂—R⁴, —C(═S)NH—R⁹, or anorganic group having 2 to 30 carbon atoms that includes at least onearomatic ring selected from a group consisting of an aromatichydrocarbon ring and a heteroaromatic ring, R³ is a substituted orunsubstituted alkyl group having 1 to 20 carbon atoms, a substituted orunsubstituted alkenyl group having 2 to 20 carbon atoms, a substitutedor unsubstituted cycloalkyl group having 3 to 12 carbon atoms, or anaromatic hydrocarbon group having 5 to 12 carbon atoms, R⁴ is an alkylgroup having 1 to 20 carbon atoms, an alkenyl group having 2 to 20carbon atoms, a phenyl group, or a 4-methylphenyl group, R⁹ is asubstituted or unsubstituted alkyl group having 1 to 20 carbon atoms, asubstituted or unsubstituted alkenyl group having 2 to 20 carbon atoms,a substituted or unsubstituted cycloalkyl group having 3 to 12 carbonatoms, or a substituted or unsubstituted aromatic group having 5 to 20carbon atoms, provided that the aromatic ring included in A^(x) andA^(y) is substituted or unsubstituted, and A^(x) and A^(y) areoptionally bonded to each other to form a ring, Y¹ to Y⁸ areindependently a chemical single bond, —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR¹—C(═O)—, —C(═O)—NR¹—, —O—C(═O)—NR¹—, —NR¹—C(═O)—O—,—NR¹—C(═O)—NR¹—, —O—NR¹—, or —NR¹—O—, R¹ is a hydrogen atom or an alkylgroup having 1 to 6 carbon atoms, G¹ and G² are independently asubstituted or unsubstituted divalent linear aliphatic group having 1 to20 carbon atoms that optionally includes —O—, —S—, —O—C(═O)—, —C(═O)—O—,—O—C(═O)—O—, —NR²—C(═O)—, —C(═O)—NR²—, —NR²—, or —C(═O)—, provided thata case where the aliphatic group includes two or more contiguous —O— or—S— is excluded, R² is a hydrogen atom or an alkyl group having 1 to 6carbon atoms, Z¹ and Z² are independently an alkenyl group having 2 to10 carbon atoms that is unsubstituted, or substituted with a halogenatom, A¹ is a substituted or unsubstituted trivalent aromatic group, A²and A³ are independently a substituted or unsubstituted divalentalicyclic hydrocarbon group having 3 to 30 carbon atoms, A⁴ and A⁵ areindependently a substituted or unsubstituted divalent aromatic grouphaving 6 to 30 carbon atoms, and Q¹ is a hydrogen atom, or a substitutedor unsubstituted alkyl group having 1 to 6 carbon atoms.
 28. A hydrazinecompound represented by any one of formulae (E), (M), (Q), (S), (U),(V), (Y), (Z), (E1), (G1), (L1), (O1), (P1), (Y1), (Z1), (A2), (B2),(C2), (D2), (E2), (F2), (H2), (I2), (J2), (R2), (S2), (T2), (U2), and(V2):